Asymmetric [2,3]-rearrangement of glycine-derived allyl ammonium ylids

The first examples of highly enantioselective [2,3]-sigmatropic rearrangements of acyclic allylic ammonium ylids are reported. Thus, a range of N-{2‘-[(N‘-allyl-N‘,N‘-dialkyl)ammonium]}acetyl camphor sultams undergo rearrangement at 0 °C in DME solution with high diastereofacial control (up to 99:1 dr) to give allylglycines in generally high yield. The power of the method has been demonstrated in a rapid and efficient synthesis of (R)-allyl glycine.

Peroxyl radical-scavenging activity of coffee brews

The ORAC(FL) assay was used in non-automated mode to evaluate the specific peroxyl radical scavenging properties of the aqueous soluble components of green and roasted Arabica and Robusta coffee samples. A relationship between ORAC(FL) and the concentration of CQAs (caffeoyl quinic acids) was found for the extracts from green coffee beans. Aqueous extracts from roasted coffee beans possessed equal or stronger scavenging power than that obtained for the green coffee beans extracts and the scavenging activity depended on the variety of coffee and the roasting conditions. Brews from Robusta coffee beans showed the highest ORAC(FL). The best scavenging properties for the brews from Arabica coffee beans were detected in samples prepared from coffee beans roasted under light conditions. The data indicate that, during roasting, a complex network of reactions takes place leading to the formation of a wide number of compounds possessing specific scavenging properties. Under mild roasting conditions, caffeoyl quinic acids appear to be the main components responsible for the free radical scavenging power of coffee brews. In contrast, Maillard reaction products may be the principal components with free radical scavenging activity in more severely (medium and dark) roasted coffees.

Investigating scaling of an abstracted LCS utilising ternary and S-Expression alphabets

Utilising the expressive power of S-Expressions in Learning Classifier Systems often prohibitively increases the search space due to increased flexibility of the endcoding. This work shows that selection of appropriate S-Expression functions through domain knowledge improves scaling in problems, as expected. It is also known that simple alphabets perform well on relatively small sized problems in a domain, e.g. ternary alphabet in the 6, 11 and 20 bit MUX domain. Once fit ternary rules have been formed it was investigated whether higher order learning was possible and whether this staged learning facilitated selection of appropriate functions in complex alphabets, e.g. selection of S-Expression functions. This novel methodology is shown to provide compact results (135-MUX) and exhibits potential for scaling well (1034-MUX), but is only a small step towards introducing abstraction to LCS.

Optimal discrimination and classification of THz spectra in the wavelet domain

In rapid scan Fourier transform spectrometry, we show that the noise in the wavelet coefficients resulting from the filter bank decomposition of the complex insertion loss function is linearly related to the noise power in the sample interferogram by a noise amplification factor. By maximizing an objective function composed of the power of the wavelet coefficients divided by the noise amplification factor, optimal feature extraction in the wavelet domain is performed. The performance of a classifier based on the output of a filter bank is shown to be considerably better than that of an Euclidean distance classifier in the original spectral domain. An optimization procedure results in a further improvement of the wavelet classifier. The procedure is suitable for enhancing the contrast or classifying spectra acquired by either continuous wave or THz transient spectrometers as well as for increasing the dynamic range of THz imaging systems. (C) 2003 Optical Society of America.

An assessment of eye-gaze potential within immersive virtual environments

In collaborative situations, eye gaze is a critical element of behavior which supports and fulfills many activities and roles. In current computer-supported collaboration systems, eye gaze is poorly supported. Even in a state-of-the-art video conferencing system such as the access grid, although one can see the face of the user, much of the communicative power of eye gaze is lost. This article gives an overview of some preliminary work that looks towards integrating eye gaze into an immersive collaborative virtual environment and assessing the impact that this would have on interaction between the users of such a system. Three experiments were conducted to assess the efficacy of eye gaze within immersive virtual environments. In each experiment, subjects observed on a large screen the eye-gaze behavior of an avatar. The eye-gaze behavior of that avatar had previously been recorded from a user with the use of a head-mounted eye tracker. The first experiment was conducted to assess the difference between users' abilities to judge what objects an avatar is looking at with only head gaze being viewed and also with eye- and head-gaze data being displayed. The results from the experiment show that eye gaze is of vital importance to the subjects, correctly identifying what a person is looking at in an immersive virtual environment. The second experiment examined whether a monocular or binocular eye-tracker would be required. This was examined by testing subjects' ability to identify where an avatar was looking from their eye direction alone, or by eye direction combined with convergence. This experiment showed that convergence had a significant impact on the subjects' ability to identify where the avatar was looking. The final experiment looked at the effects of stereo and mono-viewing of the scene, with the subjects being asked to identify where the avatar was looking. This experiment showed that there was no difference in the subjects' ability to detect where the avatar was gazing. This is followed by a description of how the eye-tracking system has been integrated into an immersive collaborative virtual environment and some preliminary results from the use of such a system.

Power properties if invariant tests for spatial autocorrelation in linear regression

This paper derives some exact power properties of tests for spatial autocorrelation in the context of a linear regression model. In particular, we characterize the circumstances in which the power vanishes as the autocorrelation increases, thus extending the work of Krämer (2005). More generally, the analysis in the paper sheds new light on how the power of tests for spatial autocorrelation is affected by the matrix of regressors and by the spatial structure. We mainly focus on the problem of residual spatial autocorrelation, in which case it is appropriate to restrict attention to the class of invariant tests, but we also consider the case when the autocorrelation is due to the presence of a spatially lagged dependent variable among the regressors. A numerical study aimed at assessing the practical relevance of the theoretical results is included

Testing for spatial autocorrelation: the regressors that make the power disappear

We show that for any sample size, any size of the test, and any weights matrix outside a small class of exceptions, there exists a positive measure set of regression spaces such that the power of the Cli-Ord test vanishes as the autocorrelation increases in a spatial error model. This result extends to the tests that dene the Gaussian power envelope of all invariant tests for residual spatial autocorrelation. In most cases, the regression spaces such that the problem occurs depend on the size of the test, but there also exist regression spaces such that the power vanishes regardless of the size. A characterization of such particularly hostile regression spaces is provided.

Precision of quasi-optical null-balanced bridge techniques for transmission and reflection coefficient measurements

The precision of quasioptical null-balanced bridge instruments for transmission and reflection coefficient measurements at millimeter and submillimeter wavelengths is analyzed. A Jones matrix analysis is used to describe the amount of power reaching the detector as a function of grid angle orientation, sample transmittance/reflectance and phase delay. An analysis is performed of the errors involved in determining the complex transmission and reflection coefficient after taking into account the quantization error in the grid angle and micrometer readings, the transmission or reflection coefficient of the sample, the noise equivalent power of the detector, the source power and the post-detection bandwidth. For a system fitted with a rotating grid with resolution of 0.017 rad and a micrometer quantization error of 1 μm, a 1 mW source, and a detector with a noise equivalent power 5×10−9 W Hz−1/2, the maximum errors at an amplitude transmission or reflection coefficient of 0.5 are below ±0.025.

Physics-based modelling for remote sensing of snow

Remote sensing is the only practicable means to observe snow at large scales. Measurements from passive microwave instruments have been used to derive snow climatology since the late 1970’s, but the algorithms used were limited by the computational power of the era. Simplifications such as the assumption of constant snow properties enabled snow mass to be retrieved from the microwave measurements, but large errors arise from those assumptions, which are still used today. A better approach is to perform retrievals within a data assimilation framework, where a physically-based model of the snow properties can be used to produce the best estimate of the snow cover, in conjunction with multi-sensor observations such as the grain size, surface temperature, and microwave radiation. We have developed an existing snow model, SNOBAL, to incorporate mass and energy transfer of the soil, and to simulate the growth of the snow grains. An evaluation of this model is presented and techniques for the development of new retrieval systems are discussed.

Monetary integration and real estate markets: an investigation of the impact of the introduction of a single currency on real estate performance

This paper assesses the impact of the monetary integration on different types of stock returns in Europe. In order to isolate European factors, the impact of global equity integration and small cap factors are investigated. European countries are sub-divided according to the process of monetary convergence. Analysis shows that national equity indices are strongly influenced by global market movements, with a European stock factor providing additional explanatory power. The global and European factors explain small cap and real estate stocks much less well –suggesting an increased importance of ‘local’ drivers. For real estate, there are notable differences between core and non-core countries. Core European countries exhibit convergence – a convergence to a European rather than a global factor. The non-core countries do not seem to exhibit common trends or movements. For the non-core countries, monetary integration has been associated with increased dispersion of returns, lower correlation and lower explanatory power of a European factor. It is concluded that this may be explained by divergence in underlying macro-economic drivers between core and non-core countries in the post-Euro period.

Measuring the impact of observations on the predictability of the Kuroshio Extension in a shallow-water model

In this paper sequential importance sampling is used to assess the impact of observations on a ensemble prediction for the decadal path transitions of the Kuroshio Extension (KE). This particle filtering approach gives access to the probability density of the state vector, which allows us to determine the predictive power — an entropy based measure — of the ensemble prediction. The proposed set-up makes use of an ensemble that, at each time, samples the climatological probability distribution. Then, in a post-processing step, the impact of different sets of observations is measured by the increase in predictive power of the ensemble over the climatological signal during one-year. The method is applied in an identical-twin experiment for the Kuroshio Extension using a reduced-gravity shallow water model. We investigate the impact of assimilating velocity observations from different locations during the elongated and the contracted meandering state of the KE. Optimal observations location correspond to regions with strong potential vorticity gradients. For the elongated state the optimal location is in the first meander of the KE. During the contracted state of the KE it is located south of Japan, where the Kuroshio separates from the coast.

The possibility of consent

Worries about the possibility of consent recall a more familiar problem about promising raised by Hume. To see the parallel here we must distinguish the power of consent from the normative significance of choice. I'll argue that we have normative interests, interests in being able to control the rights and obligations of ourselves and those around us, interests distinct from our interest in controlling the non-normative situation. Choice gets its normative significance from our non-normative control interests. By contrast, the possibility of consent depends on a species of normative interest that I'll call a permissive interest, an interest in its being the case that certain acts wrong us unless we declare otherwise. In the final section, I'll show how our permissive interests underwrite the possibility of consent.

Building a left coast: the legacy of the California Popular Front and the challenge to Cold War liberalism in the post-world war two era

The Cold War in the late 1940s blunted attempts by the Truman administration to extend the scope of government in areas such as health care and civil rights. In California, the combined weakness of the Democratic Party in electoral politics and the importance of fellow travelers and communists in state liberal politics made the problem of how to advance the left at a time of heightened Cold War tensions particularly acute. Yet by the early 1960s a new generation of liberal politicians had gained political power in the Golden State and was constructing a greatly expanded welfare system as a way of cementing their hold on power. In this article I argue that the New Politics of the 1970s, shaped nationally by Vietnam and by the social upheavals of the 1960s over questions of race, gender, sexuality, and economic rights, possessed particular power in California because many activists drew on the longer-term experiences of a liberal politics receptive to earlier anti-Cold War struggles. A desire to use political involvement as a form of social networking had given California a strong Popular Front, and in some respects the power of new liberalism was an offspring of those earlier battles.

‘Souvenirs, souvenirs': the role of memory in the work of Annie Saumont

The work of nouvelliste Annie Saumont constantly explores the phenomenon of memory, and of memories. This article identifies and nuances the various forms that this exploration takes. An introductory contextualization of author and theme is followed by the presentation of a short story, ‘Méandres’, which embodies the first quality of memory to be examined: its capacity not only to recall but also to re-evaluate a past which is thus shown to be as hypothetical as the future. Memory as guilt that moulds or puts its indelible stamp on lives is then evoked by means of examples from other stories, illustrating the gradations Saumont achieves in her investigation of the power of this complex faculty. The next section turns to her portrayal of involuntary memory. Unlike for Proust, the instances of spontaneous remembering that are experienced by her characters lunge at them down the years almost exclusively to wound or disorientate. Depictions of the memory which conserves, and is thus burdened by, secrets are then considered, and finally Saumont's evocation of characters who have different reasons to analyse the way their own and other people's memories work. The conclusion to be drawn is that for Saumont, we are our memories; the ability to master a ‘judicious interpretation’ of memory – or indeed, to forget – is, in her stories, overwhelmingly a quality to be envied.

Cheap dates and the delusion of gratification: are votes sold or traded in the EU Council of Ministers?

Each year, small Member States receive a disproportionate share of the European Union's (EU's) budget. A prominent explanation for this is that Council decision-making involves a healthy dose of vote selling, whereby large Member States offer small states generous fiscal transfers in exchange for influence over policy. But nobody has investigated whether net budget contributors actually get anything for their money. In this paper I identify the vote selling model's observable implications and find virtually no evidence consistent with Council cash-for-votes exchanges. I also show that a compromise model – the leading model of EU decision-making to date – modified to incorporate vote selling does not outperform a standard one that assumes votes are traded rather than sold. Taken together, the results suggest that Council decision-making operates with little or no vote selling, and that regardless of whatever they think they might be buying, net budget contributors get little or nothing in return for their money. These findings call for further investigation into how Member States approach the issue of fiscal transfers, and into the factors other than formal voting weight that affect the power of actors engaged in EU decision-making.