Total synthesis of (+/-) maculalactone A, maculalactone B and maculalactone C and the determination of the absolute configuration of natural (+) maculalactone A by asymmetric synthesis

Maculalactones A, B and C from the marine cyanobacterium Kyrtuthrix maculans are amongst the only compounds based on the tribenzylbutyrolactone skeleton known in nature and (+) maculalactone A from the natural source possesses significant biological activity against various marine herbivores and marine settlers. We now report a concise synthesis of racemic maculalactone A in five steps from inexpensive starting materials. Maculalactones B and C were synthesized by a minor modification to this procedure, and the synthetic design also permitted an asymmetric synthesis of maculalactone A to be achieved in around 85% ee. The (+) and (-) enantiomers of maculalactone A were assigned, respectively, to the S and R configurations on the basis of the chiral selectivity expected for catecholborane reduction of an unsymmetrical ketone in the presence of Corey's oxazoborolidine catalyst. Surprisingly, it appeared that natural (+) maculalactone A was biosynthesized in K. maculans in a partially racemic form, comprising ca. 90-95% of the (S) enantiomer and 5-10% of its (R) enantiomer. Coincidentally therefore, the percentage enantiomeric excess of the product obtained from asymmetric synthesis almost exactly matched that found in nature. (C) 2004 Elsevier Ltd. All rights reserved.

The effect of flow field & geometry on the dynamic contact angle

A number of recent experiments suggest that, at a given wetting speed, the dynamic contact angle formed by an advancing liquid-gas interface with a solid substrate depends on the flow field and geometry near the moving contact line. In the present work, this effect is investigated in the framework of an earlier developed theory that was based on the fact that dynamic wetting is, by its very name, a process of formation of a new liquid-solid interface (newly “wetted” solid surface) and hence should be considered not as a singular problem but as a particular case from a general class of flows with forming or/and disappearing interfaces. The results demonstrate that, in the flow configuration of curtain coating, where a liquid sheet (“curtain”) impinges onto a moving solid substrate, the actual dynamic contact angle indeed depends not only on the wetting speed and material constants of the contacting media, as in the so-called slip models, but also on the inlet velocity of the curtain, its height, and the angle between the falling curtain and the solid surface. In other words, for the same wetting speed the dynamic contact angle can be varied by manipulating the flow field and geometry near the moving contact line. The obtained results have important experimental implications: given that the dynamic contact angle is determined by the values of the surface tensions at the contact line and hence depends on the distributions of the surface parameters along the interfaces, which can be influenced by the flow field, one can use the overall flow conditions and the contact angle as a macroscopic multiparametric signal-response pair that probes the dynamics of the liquid-solid interface. This approach would allow one to investigate experimentally such properties of the interface as, for example, its equation of state and the rheological properties involved in the interface’s response to an external torque, and would help to measure its parameters, such as the coefficient of sliding friction, the surface-tension relaxation time, and so on.

Tropical and extratropical responses of the North Atlantic atmospheric circulation to a sustained weakening of the MOC

The tropospheric response to a forced shutdown of the North Atlantic Ocean’s meridional overturning circulation (MOC) is investigated in a coupled ocean–atmosphere GCM [the third climate configuration of the Met Office Unified Model (HadCM3)]. The strength of the boreal winter North Atlantic storm track is significantly increased and penetrates much farther into western Europe. The changes in the storm track are shown to be consistent with the changes in near-surface baroclinicity, which can be linked to changes in surface temperature gradients near regions of sea ice formation and in the open ocean. Changes in the SST of the tropical Atlantic are linked to a strengthening of the subtropical jet to the north, which, combined with the enhanced storm track, leads to a pronounced split in the jet structure over Europe. EOF analysis and stationary box indices methods are used to analyze changes to the North Atlantic Oscillation (NAO). There is no consistent signal of a change in the variability of the NAO, and while the changes in the mean flow project onto the positive NAO phase, they are significantly different from it. However, there is a clear eastward shift of the NAO pattern in the shutdown run, and this potentially has implications for ocean circulation and for the interpretation of proxy paleoclimate records.

Parallel genetic algorithms for the tuning of a fuzzy AQM controller

This paper presents the results of the application of a parallel Genetic Algorithm (GA) in order to design a Fuzzy Proportional Integral (FPI) controller for active queue management on Internet routers. The Active Queue Management (AQM) policies are those policies of router queue management that allow the detection of network congestion, the notification of such occurrences to the hosts on the network borders, and the adoption of a suitable control policy. Two different parallel implementations of the genetic algorithm are adopted to determine an optimal configuration of the FPI controller parameters. Finally, the results of several experiments carried out on a forty nodes cluster of workstations are presented.

The two-dimensional anharmonic oscillator I: vibration-rotation constants of fulminic acid, HCNO

The lowest-wavenumber vibration of HCNO and DCNO, ν5, is known to involve a largeamplitude low-frequency anharmonic bending of the CH bond against the CNO frame. In this paper the anomalous vibrational dependence of the observed rotational constants B(v5, l5), and of the observed l-doubling interactions, is interpreted according to a simple effective vibration-rotation Hamiltonian in which the appropriate vibrational operators are averaged in an anharmonic potential surface over the normal coordinates (Q5x, Q5y). All of the data on both isotopes are interpreted according to a single potential surface having a minimum energy at a slightly bent configuration of the HCN angle ( 170°) with a maximum at the linear configuration about 2 cm−1 higher. The other coefficients in the Hamiltonian are also interpreted in terms of the structure and the harmonic and anharmonic force fields; the substitution structure at the “hypothetical linear configuration” determined in this way gives a CH bond length of 1.060 Å, in contrast to the value 1.027 Å determined from the ground-state rotational constants. We also discuss the difficulties in rationalizing our effective Hamiltonian in terms of more fundamental theory, as well as the success and limitations of its use in practice.

A regime view of the North Atlantic Oscillation and its response to anthropogenic forcing

The distribution of the daily wintertime North Atlantic Oscillation (NAO) index in the 40-yr ECMWF Re-Analysis (ERA-40) is significantly negatively skewed. Dynamical and statistical analyses both suggest that this skewness reflects the presence of two distinct regimes—referred to as “Greenland blocking” and “subpolar jet.” Changes in both the relative occurrence and in the structure of the regimes are shown to contribute to the long-term NAO trend over the ERA-40 period. This is contrasted with the simulation of the NAO in 100-yr control and doubled CO2 integrations of the third climate configuration of the Met Office Unified Model (HadCM3). The model has clear deficiencies in its simulation of the NAO in the control run, so its predictions of future behavior must be treated with caution. However, the subpolar jet regime does become more dominant under anthropogenic forcing and, while this change is small it is clearly statistically significant and does represent a real change in the nature of NAO variability in the model.

The effects of paeonol on the electrophysiological properties of cardiac ventricular myocytes

Previous studies have shown that "Mudanpi", a Chinese herbal medicine, has a significant cardioprotective effect against myocardial ischaemia. Based on these findings we hypothesised that paeonol, the main component of Mudanpi, might have an effect on the cellular electrophysiology of cardiac ventricular myocytes. The effects of paeonol on the action potential and ion channels of cardiac ventricular myocytes were studied using the standard whole-cell configuration of the patch-clamp technique. Ventricular myocytes were isolated from the hearts of adult guinea-pig by enzymic dispersion. The myocytes were continuously perfused with various experimental solutions at room temperature and paeonol applied in the perfusate. Action potentials and membrane currents were recorded using both current and voltage clamp modes of the patch-clamp technique. Paeonol, at concentrations 160 mu M and 640 mu M, decreased the action potential upstroke phase, an action associated with the blockade of the voltage-gated, fast sodium channel. The effects of paeonol on both action potential and Na+ current were concentration dependent. Paeonol had a high affinity for inactivated sodium channels. Paeonol also shortened the action potential duration, in a manner not associated with the blockade of the calcium current, or the enhancement of potassium currents. These findings suggest that paeonol, and therefore Mudanpi, may possess antiarrhythmic activity, which may confer its cardioprotective effects. (c) 2006 Elsevier B.V All rights reserved.

Aldol reaction of butane-2,3-diacetal protected methyl glycerate

The addition of aldehydes to butane-2,3-diacetal has been investigated. The reaction was shown to be both regioselective and diastereoselective by 1H NMR spectroscopy. The configuration of the newly formed stereocenter was determined by Mosher’s ester analysis.

Sensitivity of GCM tropical middle atmosphere variability and climate to ozone and parametrized gravity wave changes

This paper describes the impact of changing the current imposed ozone climatology upon the tropical Quasi-Biennial Oscillation (QBO) in a high top climate configuration of the Met Office U.K. general circulation model. The aim is to help distinguish between QBO changes in chemistry climate models that result from temperature-ozone feedbacks and those that might be forced by differences in climatology between previously fixed and newly interactive ozone distributions. Different representations of zonal mean ozone climatology under present-day conditions are taken to represent the level of change expected between acceptable model realizations of the global ozone distribution and thus indicate whether more detailed investigation of such climatology issues might be required when assessing ozone feedbacks. Tropical stratospheric ozone concentrations are enhanced relative to the control climatology between 20–30 km, reduced from 30–40 km and enhanced above, impacting the model profile of clear-sky radiative heating, in particular warming the tropical stratosphere between 15–35 km. The outcome is consistent with a localized equilibrium response in the tropical stratosphere that generates increased upwelling between 100 and 4 hPa, sufficient to account for a 12 month increase of modeled mean QBO period. This response has implications for analysis of the tropical circulation in models with interactive ozone chemistry because it highlights the possibility that plausible changes in the ozone climatology could have a sizable impact upon the tropical upwelling and QBO period that ought to be distinguished from other dynamical responses such as ozone-temperature feedbacks.

Effect of dextransucrase cellobiose acceptor products on the growth of human gut bacteria

The selective fermentation by human gut bacteria of gluco-oligosaccharides obtained from the reaction between the glucosyl group of sucrose and cellobiose, catalyzed by dextransucrases (DSR) from Leuconostoc mesenteroides, has been evaluated. Oligosaccharides were fractionated according to their molecular weight, and their effect on the growth of different bacterial groups was studied. To determine the structure (position and configuration of glycosidic linkages)�function relationship, their properties were compared to those of DSR maltose acceptor products (DSRMal) and of recognized prebiotic carbohydrates (fructo-oligosaccharides, FOS). Cellobiose acceptor products (DSRCel) showed bifidogenic properties similar to those of FOS. However, no significant differences related to molecular weight or isomeric configurations were found for DSRCel and DSRMal products.

The basic ingredients of the North Atlantic Storm Track. Part II: Sea surface temperatures

The impact of North Atlantic SST patterns on the storm track is investigated using a hierarchy of GCM simulations using idealized (aquaplanet) and “semirealistic” boundary conditions in the atmospheric component (HadAM3) of the third climate configuration of the Met Office Unified Model (HadCM3). This framework enables the mechanisms determining the tropospheric response to North Atlantic SST patterns to be examined, both in isolation and in combination with continental-scale landmasses and orography. In isolation, a “Gulf Stream” SST pattern acts to strengthen the downstream storm track while a “North Atlantic Drift” SST pattern weakens it. These changes are consistent with changes in the extratropical SST gradient and near-surface baroclinicity, and each storm-track response is associated with a consistent change in the tropospheric jet structure. Locally enhanced near-surface horizontal wind convergence is found over the warm side of strengthened SST gradients associated with ascending air and increased precipitation, consistent with previous studies. When the combined SST pattern is introduced into the semirealistic framework (including the “North American” continent and the “Rocky Mountains”), the results suggest that the topographically generated southwest–northeast tilt in the North Atlantic storm track is enhanced. In particular, the Gulf Stream shifts the storm track south in the western Atlantic whereas the strong high-latitude SST gradient in the northeastern Atlantic enhances the storm track there.

The island and the world: kinship, friendship and living together in selected writings of Sam Selvon

This article argues that the ethical force of Trinidadian Sam Selvon’s creative writings comes from the particular configuration of living together that he is interested in, both in his Trinidadian novels and his London ones. It reads examples of this living together alongside and in difference that emerges through his focus on the relations between neighbours, friends and lovers, rather than the kinship relations of family. It argues that his works thereby map horizontal zones of attachment and possible solidarities across groupings that reconfigure vertically inscribed genealogical paradigms of belonging to place and each other based on models of historical continuity and inheritance.

The President above parties: a founding illusion of the Fifth Republic

De Gaulle, founder of the Fifth French Republic, cherished the notion that the president of the Republic could somehow stand above party politics. In many ways this belief shaped the early institutional configuration of the new Republic. Party politics, however, rapidly reached the presidency, especially with the move, under the constitutional reform of 1962, to direct election of the president. This article charts the development of France's 'political constitution' and the relationship between president and parties over the first decade of the Fifth Republic. It finds that although the presidency became the prime goal of party political competition, the (often dysfunctional) illusion of a head of state above politics continues to shape the behaviour and perceptions of French presidents.

An evaluation of the spatiotemporal structure of large-scale European drought within the HiGEM climate model

We compare the characteristics of synthetic European droughts generated by the HiGEM1 coupled climate model run with present day atmospheric composition with observed drought events extracted from the CRU TS3 data set. The results demonstrate consistency in both the rate of drought occurrence and the spatiotemporal structure of the events. Estimates of the probability density functions for event area, duration and severity are shown to be similar with confidence > 90%. Encouragingly, HiGEM is shown to replicate the extreme tails of the observed distributions and thus the most damaging European drought events. The soil moisture state is shown to play an important role in drought development. Once a large-scale drought has been initiated it is found to be 50% more likely to continue if the local soil moisture is below the 40th percentile. In response to increased concentrations of atmospheric CO2, the modelled droughts are found to increase in duration, area and severity. The drought response can be largely attributed to temperature driven changes in relative humidity. 1 HiGEM is based on the latest climate configuration of the Met Office Hadley Centre Unified Model (HadGEM1) with the horizontal resolution increased to 1.25 x 0.83 degrees in longitude and latitude in the atmosphere and 1/3 x 1/3 degrees in the ocean.