Asymmetric synthesis using catalysts containing multiple stereogenic centres and a trans-1,2-diaminocyclohexane core; reversal of predominant enantioselectivity upon N-alkylation

N-Methylation of ligands containing a trans-1,2-diaminocyclohexane core and multiple stereogenic centres is shown to provide the product of the opposite configuration in significant enantiomeric excess, in the addition of diethylzinc to aldehydes. Some of the ligands were effective in an asymmetric Michael addition. (C) 2004 Elsevier Ltd. All rights reserved.

A low clock frequency FFT core implementation for multiband full-rate ultra-wideband (UWB) receivers

This paper discusses the design, implementation and synthesis of an FFT module that has been specifically optimized for use in the OFDM based Multiband UWB system, although the work is generally applicable to many other OFDM based receiver systems. Previous work has detailed the requirements for the receiver FFT module within the Multiband UWB ODFM based system and this paper draws on those requirements coupled with modern digital architecture principles and low power design criteria to converge on our optimized solution particularly aimed at a low-clock rate implementation. The FFT design obtained in this paper is also applicable for implementation of the transmitter IFFT module therefore only needing one FFT module in the device for half-duplex operation. The results from this paper enable the baseband designers of the 200Mbit/sec variant of Multiband UWB systems (and indeed other OFDM based receivers) using System-on-Chip (SoC), FPGA and ASIC technology to create cost effective and low power consumer electronics product solutions biased toward the very competitive market.

Radiative efficiencies and global warming potentials using theoretically determined absorption cross-sections for several hydrofluoroethers (HFEs) and hydrofluoropolyethers (HFPEs)

Integrated infrared cross-sections and wavenumber positions for the vibrational modes of a range of hydrofluoroethers (HFEs) and hydrofluoropolyethers (HFPEs) have been calculated. Spectra were determined using a density functional method with an empirically derived correction for the wavenumbers of band positions. Radiative efficiencies (REs) were determined using the Pinnock et al. method and were used with atmospheric lifetimes from the literature to determine global warming potentials (GWPs). For the HFEs and the majority of the molecules in the HG series HFPEs, theoretically determined absorption cross-sections and REs lie within ca. 10% of those determined using measured spectra. For the larger molecules in the HG series and the HG′ series of HFPEs, agreement is less good, with theoretical values for the integrated cross-sections being up to 35% higher than the experimental values; REs are up to 45% higher. Our method gives better results than previous theoretical approaches, because of the level of theory chosen and, for REs, because an empirical wavenumber correction derived for perfluorocarbons is effective in predicting the positions of C–F stretching frequencies at around 1250 cm−1 for the molecules considered here.

Does training improve understanding of core concepts in cognitive behaviour therapy by people with intellectual disabilities? A randomized experiment

Background. People with intellectual disabilities (ID) experience similar or even higher rates of mental health problems than the general population and there is a need to develop appropriate treatments. Cognitive behaviour therapy (CBT) is effective for a wide range of disorders in the general population. However, there is some evidence that people with ID may lack the cognitive skills needed to take part in CBT. Aims. To test if people with ID can learn skills required for CBT, specifically the ability to distinguish between thoughts, feelings, and behaviours and to link thoughts and feelings (cognitive mediation). Method. A randomized independent groups design was used to examine the effect of training in CBT on two tasks measuring CBT skills. Thirty-four adults with ID were randomly allocated to the experimental condition ðN ¼ 18Þ or to the control condition ðN ¼ 16Þ. CBT skills were assessed blind at baseline and after the intervention. Results. The training led to significant improvements in participants’ ability to link thoughts and feelings, and this skill was generalized to new material. There was no effect of training on participants’ ability to distinguish amongst thoughts, feelings, and behaviours. People with ID can, therefore, learn some skills required for CBT. This implies that preparatory training for CBT might be useful for people with ID. The results might be applicable to other groups who find aspects of CBT difficult.

Loss potentials associated with European windstorms under future climate conditions

Possible changes in the frequency and intensity of windstorms under future climate conditions during the 21st century are investigated based on an ECHAM5 GCM multi-scenario ensemble. The intensity of a storm is quantified by the associated estimated loss derived with using an empirical model. The geographical focus is ‘Core Europe’, which comprises countries of Western Europe. Possible changes of losses are analysed by comparing ECHAM5 GCM data for recent (20C, 1960 to 2000) and future climate conditions (B1, A1B, A2; 2060 to 2100), each with 3 ensemble members. Changes are quantified using both rank statistics and return periods (RP) estimated by fitting an extreme value distribution using the peak over threshold method to potential storm losses. The estimated losses for ECHAM5 20C and reanalysis events show similar statistical features in terms of return periods. Under future climate conditions, all climate scenarios show an increase in both frequency and magnitude of potential losses caused by windstorms for Core Europe. Future losses that are double the highest ECHAM5 20C loss are identified for some countries. While positive changes of ranking are significant for many countries and multiple scenarios, significantly shorter RPs are mostly found under the A2 scenario for return levels correspondent to 20 yr losses or less. The emergence time of the statistically significant changes in loss varies from 2027 to 2100. These results imply an increased risk of occurrence of windstorm-associated losses, which can be largely attributed to changes in the meteorological severity of the events. Additionally, factors such as changes in the cyclone paths and in the location of the wind signatures relative to highly populated areas are also important to explain the changes in estimated losses.