Asymmetric aziridine synthesis by aza-Darzens reaction of N-diphenylphosphinylimines with chiral enolates. Part 1: formation of cis-aziridines

Theaza-Darzens ('ADZ') reactions off-diphenylphosphinyl (W-Dpp') imines with chiral enolates derived from oxazolidinones and camphorsultam have been Studied. Whilst oxazolidinone enolates reacted poorly in terms of aziridination, the use of the chiral enolate derived from both antipodes of N-bromoacetyl 2, 10-camphorsultam, 2R-(5) and 2S-(5), with N-diphehenylphosphinyl aryl and tert-butylimines proceeded in generally good yield to give, respectively, (2'R,3'R)- or (2'S,3'S)-cis-N-diphenylphosphinyl aziridinoyl sultams of high de. (c) 2006 Elsevier Ltd. All rights reserved.

Building cluster and shading in urban canyon for hot dry climate - Part 1: Air and surface temperature measurements

Under low latitude conditions, minimization of solar radiation within the urban environment may often be a desirable criterion in urban design. The dominance of the direct component of the global solar irradiance under clear high sun conditions requires that the street solar access must be small. It is well known that the size and proportion of open spaces has a great influence on the urban microclimate This paper is directed towards finding the interaction between urban canyon geometry and incident solar radiation. The effect of building height and street width on the shading of the street surfaces and ground for different orientations have been examined and evaluated. It is aimed to explore the extent to which these parameters affect the temperature in the street. This work is based on air and surface temperature measurements taken in different urban street canyons in EL-Oued City (hot and and climate), Algeria. In general, the results show that there are less air temperature variations compared to the surface temperature which really depends on the street geometry and sky view factor. In other words, there is a big correlation between the street geometry, sky view factor and surface temperatures.

Building cluster and shading in urban canyon for hot dry climate Part 2: Shading simulations

Under low latitude conditions, minimisation of solar irradiance within the urban environment may often be an important criterion in urban design. This can be achieved when the obstruction angle is large (high H/W ratio, H = height, W = width). Solar access to streets can always be decreased by increasing H/W to larger values. It is shown in this paper that the street canyon orientation (and not only the H/W ratio) has a considerable effect on solar shading and urban microclimate. The paper demonstrates through a series of shading simulation and temperature measurements that a number of useful relationships can be developed between the geometry and the microclimate of urban street canyons. These relationships are potentially helpful to assist in the formulation of urban design guidelines governing street dimensions and orientations for use by urban designers.

Torque in mooring chain. Part 1: Background and theory

Chain in both its forms - common (or stud-less) and stud-link - has many engineering applications. It is widely used as a component in the moorings of offshore floating systems, where its ruggedness and corrosion resistance make it an attractive choice. Chain exhibits some interesting behaviour in that when straight and subject to an axial load it does not twist or generate any torque, but if twisted or loaded when in a twisted condition it behaves in a highly non-linear manner, with the torque dependent upon the level of twist and axial load. Clearly an understanding of the way in which chains may behave and interact with other mooring components (such as wire rope, which also exhibits coupling between axial load and generated torque) when they are in service is essential. However, the sizes of chain that are in use in offshore moorings (typical bar diameters are 75 mm and greater) are too large to allow easy testing. This paper, which is in two parts, aims to address the issues and considerations relevant to torque in mooring chain. The first part introduces a frictionless theory that predicts the resultant torques and 'lift' in the links as non-dimensionalized functions of the angle of twist. Fortran code is presented in an Appendix, which allows the reader to make use of the analysis. The second part of the paper presents results from experimental work on both stud-less (41 mm) and stud-link (20.5 and 56 mm) chains. Torsional data are presented in both 'constant twist' and 'constant load' forms, as well as considering the lift between the links.

Torque in mooring chain. Part 2: Experimental investigation

Chain is a commonly used component in offshore moorings where its ruggedness and corrosion resistance make it an attractive choice. Another attractive property is that a straight chain is inherently torque balanced. Having said this, if a chain is loaded in a twisted condition, or twisted when under load, it exhibits highly non-linear torsional behaviour. The consequences of this behaviour can cause handling difficulties or may compromise the integrity of the mooring system, and care must be taken to avoid problems for both the chain and any components to which it is connected. Even with knowledge of the potential problems, there will always be occasions where, despite the utmost care, twist is unavoidable. Thus it is important for the engineer to be able to determine the effects. A frictionless theory has been developed in Part 1 of the paper that may be used to predict the resultant torques and movement or 'lift' in the links as non-dimensional functions of the angle of twist. The present part of the paper describes a series of experiments undertaken on both studless and stud-link chain to allow comparison of this theoretical model with experimental data. Results are presented for the torsional response and link lift for 'constant twist' and 'constant load' type tests on chains of three different link sizes.

Functional food, blood lipids and cardiovascular disease. Part 1: probiotics

For the past 20 years, the focuses of public health strategies for reducing the risk of cardiovascular disease (CVD) have been aimed at lowering cholesterol levels. However recent findings have highlighted not only cholesterol but also triacylglycerol as a lipid risk factor for CVD. Dietary strategies which are able to reduce these circulating lipid levels, but which are able to offer long-term efficacy comparable with effective drug treatments, are currently being sought. One dietary strategy that has been proposed to benefit the lipid profile involves the supplementation of the diet with probiotics (Part 1), prebiotics and synbiotics (Part 2), which are mechanisms to improve the health of the host by supplementation and/or fortification of certain health promoting gut bacteria. Probiotics in the form of fermented milk products have been shown to have cholesterol-lowering properties, whereas non-digestible fermentable prebiotics have been shown to reduce triacylglycerol levels in animal studies. However in humans studies, there have been inconsistent findings with respect to changes in lipid levels with both prebiotics and probiotics although on the whole there have been favourable outcomes.

Water-soluble precursors of beef flavour. Part II: effect of post-mortem conditioning

Changes in glycolytic metabolites, nucleotide degradation products, free amino acids and other amino compounds were monitored in beef muscle (M. longissimus lumborum), stored for 21 days at 4 degrees C, in order to evaluate how post-mortem conditioning may affect flavour formation in beef. The major effects observed in sugar-related substances were the dephosphorylation of the phosphates of glucose, fructose and mannose, to yield their free sugars, as well as the breakdown of inosine 5'-monophosphate, to give a sixfold increase in ribose. Total reducing sugars increased by only 15% during conditioning, while glycogen levels remained unchanged from 2 days post-slaughter. Free amino acids increased during conditioning, particularly between days 7 and 14. Phenylalanine, methionine, lysine, leucine and isoleucine were the amino acids showing the greatest increase with conditioning time, with methionine, in particular, showing a sevenfold increase during the conditioning period. The effects of these precursor changes on cooked beef flavour are discussed. (c) 2007 Elsevier Ltd. All rights reserved.

Functional food, blood lipids and cardiovascular disease. Part 2: prebiotics and synbiotics

For the past 20 years, the focuses of public health strategies for reducing the risk of cardiovascular disease (CVD) have been aimed at lowering cholesterol levels. However, recent findings have highlighted not only cholesterol but also triacylglycerol as a lipid risk factor for CVD. Dietary strategies which are able to reduce these Circulating lipid levels, but which are able to offer longterm efficacy comparable with effective drug treatments, are currently being sought. One dietary strategy that has been proposed to benefit the lipid profile involves the supplementation of the diet with probiotics (Part 1) prebiotics and synbiotics (Part 2), which are mechanisms to improve the health of the host by supplementation and/or fortification of certain health promoting gut bacteria. Probiotics in the form of fermented milk products have been shown to have cholesterol-lowering properties, whereas non-digestible fermentable prebiotics have been shown to reduce triacylglycerol levels in animal studies, However, in human studies, there have been inconsistent findings with respect to changes in lipid levels with both prebiotics and probiotics although on the whole there have been favourable outcomes.

Modelling the effect of fatty acids in odour development of cooked meat in vitro: part I - sensory perception

We have investigated the contribution of muscle components to the development of cooked meat odour in an aqueous model system using trained taste panels. Reaction mixtures were prepared with oleic, linoleic and linolenic acids with or without cysteine and ribose in a buffer with or without ferrous sulphate. Odour profiles were assessed and triangular tests were used to determine the ability of panellists to discriminate between mixtures. The presence of sugar and amino acid was highly detectable by panellists independently of the fatty acid considered (P < 0.001). However, the presence of C18:3 made differences. more obvious between mixtures than the presence of C18:1 or C18:2. `Meaty' notes were only associated with cysteine and ribose. `Fishy' notes were only apparent in C18:3 mixtures with or without sugar and amino acid, although the presence of cysteine and ribose decreased the perception. The addition of Fe+ +, a pro-oxidant present in the muscle, produced a reduction in the score of the attributes although the pattern was the same as when Fe was not used in the mixtures. Only `fishy' notes that were exclusively perceived in C18:3 mixtures showed a higher score in the presence of iron. Iron also produced a better discrimination in C18:3 mixtures, which were closely related to `grassy' notes in the presence of cysteine and ribose. (C) 2002 Published by Elsevier Science Ltd.

Femtosecond evolution of spatially inhomogeneous carrier excitations: part 2: stochastic approach and GRID implementation

We present a stochastic approach for solving the quantum-kinetic equation introduced in Part I. A Monte Carlo method based on backward time evolution of the numerical trajectories is developed. The computational complexity and the stochastic error are investigated numerically. Variance reduction techniques are applied, which demonstrate a clear advantage with respect to the approaches based on symmetry transformation. Parallel implementation is realized on a GRID infrastructure.

Effect of improving representation of horizontal and vertical cloud structure on the Earth's global radiation budget. Part I: review and parametrization

A poor representation of cloud structure in a general circulation model (GCM) is widely recognised as a potential source of error in the radiation budget. Here, we develop a new way of representing both horizontal and vertical cloud structure in a radiation scheme. This combines the ‘Tripleclouds’ parametrization, which introduces inhomogeneity by using two cloudy regions in each layer as opposed to one, each with different water content values, with ‘exponential-random’ overlap, in which clouds in adjacent layers are not overlapped maximally, but according to a vertical decorrelation scale. This paper, Part I of two, aims to parametrize the two effects such that they can be used in a GCM. To achieve this, we first review a number of studies for a globally applicable value of fractional standard deviation of water content for use in Tripleclouds. We obtain a value of 0.75 ± 0.18 from a variety of different types of observations, with no apparent dependence on cloud type or gridbox size. Then, through a second short review, we create a parametrization of decorrelation scale for use in exponential-random overlap, which varies the scale linearly with latitude from 2.9 km at the Equator to 0.4 km at the poles. When applied to radar data, both components are found to have radiative impacts capable of offsetting biases caused by cloud misrepresentation. Part II of this paper implements Tripleclouds and exponential-random overlap into a radiation code and examines both their individual and combined impacts on the global radiation budget using re-analysis data.

Effect of improving representation of horizontal and vertical cloud structure on the Earth's global radiation budget. Part II: The global effects

Reliably representing both horizontal cloud inhomogeneity and vertical cloud overlap is fundamentally important for the radiation budget of a general circulation model. Here, we build on the work of Part One of this two-part paper by applying a pair of parameterisations that account for horizontal inhomogeneity and vertical overlap to global re-analysis data. These are applied both together and separately in an attempt to quantify the effects of poor representation of the two components on radiation budget. Horizontal inhomogeneity is accounted for using the “Tripleclouds” scheme, which uses two regions of cloud in each layer of a gridbox as opposed to one; vertical overlap is accounted for using “exponential-random” overlap, which aligns vertically continuous cloud according to a decorrelation height. These are applied to a sample of scenes from a year of ERA-40 data. The largest radiative effect of horizontal inhomogeneity is found to be in areas of marine stratocumulus; the effect of vertical overlap is found to be fairly uniform, but with larger individual short-wave and long-wave effects in areas of deep, tropical convection. The combined effect of the two parameterisations is found to reduce the magnitude of the net top-of-atmosphere cloud radiative forcing (CRF) by 2.25 W m−2, with shifts of up to 10 W m−2 in areas of marine stratocumulus. The effects of the uncertainty in our parameterisations on radiation budget is also investigated. It is found that the uncertainty in the impact of horizontal inhomogeneity is of order ±60%, while the uncertainty in the impact of vertical overlap is much smaller. This suggests an insensitivity of the radiation budget to the exact nature of the global decorrelation height distribution derived in Part One.