Temperature- and Pressure-induced Proton Transfer in the 1:1 Adduct Formed between Squaric Acid and 4,4 '-Bipyridine

We have applied a combination of spectroscopic and diffraction methods to study the adduct formed between squaric acid and bypridine, which has been postulated to exhibit proton transfer associated with a single-crystal to single-crystal phase transition at ca. 450 K. A combination of X-ray single-crystal and very-high flux powder neutron diffraction data confirmed that a proton does transfer from the acid to the base in the high-temperature form. Powder X-ray diffraction measurements demonstrated that the transition was reversible but that a significant kinetic energy barrier must be overcome to revert to the original structure. Computational modeling is consistent with these results. Modeling also revealed that, while the proton transfer event would be strongly discouraged in the gas phase, it occurs in the solid state due to the increase in charge state of the molecular ions and their arrangement inside the lattice. The color change is attributed to a narrowing of the squaric acid to bipyridine charge-transfer energy gap. Finally, evidence for the possible existence of two further phases at high pressure is also presented.

Estimating uncertainty in terrestrial critical loads and their exceedances at four sites in the UK

Critical loads are the basis for policies controlling emissions of acidic substances in Europe and elsewhere. They are assessed by several elaborate and ingenious models, each of which requires many parameters, and have to be applied on a spatially-distributed basis. Often the values of the input parameters are poorly known, calling into question the validity of the calculated critical loads. This paper attempts to quantify the uncertainty in the critical loads due to this "parameter uncertainty", using examples from the UK. Models used for calculating critical loads for deposition of acidity and nitrogen in forest and heathland ecosystems were tested at four contrasting sites. Uncertainty was assessed by Monte Carlo methods. Each input parameter or variable was assigned a value, range and distribution in an objective a fashion as possible. Each model was run 5000 times at each site using parameters sampled from these input distributions. Output distributions of various critical load parameters were calculated. The results were surprising. Confidence limits of the calculated critical loads were typically considerably narrower than those of most of the input parameters. This may be due to a "compensation of errors" mechanism. The range of possible critical load values at a given site is however rather wide, and the tails of the distributions are typically long. The deposition reductions required for a high level of confidence that the critical load is not exceeded are thus likely to be large. The implication for pollutant regulation is that requiring a high probability of non-exceedance is likely to carry high costs. The relative contribution of the input variables to critical load uncertainty varied from site to site: any input variable could be important, and thus it was not possible to identify variables as likely targets for research into narrowing uncertainties. Sites where a number of good measurements of input parameters were available had lower uncertainties, so use of in situ measurement could be a valuable way of reducing critical load uncertainty at particularly valuable or disputed sites. From a restricted number of samples, uncertainties in heathland critical loads appear comparable to those of coniferous forest, and nutrient nitrogen critical loads to those of acidity. It was important to include correlations between input variables in the Monte Carlo analysis, but choice of statistical distribution type was of lesser importance. Overall, the analysis provided objective support for the continued use of critical loads in policy development. (c) 2007 Elsevier B.V. All rights reserved.

Reprogramming the cell cycle machinery to treat cardiovascular disease

Coronary artery disease is one of the most common heart pathologies. Restriction of blood flow to the heart by atherosclerotic lesions, leading to angina pectoris and myocardial infarction, damages the heart, resulting in impaired cardiac function. Damaged myocardium is replaced by scar tissue since surviving cardiomyocytes are unable to proliferate to replace lost heart tissue. Although narrowing of the coronary arteries can be treated successfully using coronary revascularisation procedures, re-occlusion of the treated vessels remains a significant clinical problem. Cell cycle control mechanisms are key in both the impaired cardiac repair by surviving cardiomyocytes and re-narrowing of treated vessels by maladaptive proliferation of vascular smooth muscle cells. Strategies targeting the cell cycle machinery in the heart and vasculature offer promise both for the improvement of cardiac repair following MI and the prevention of restenosis and bypass graft failure following revascularisation procedures.

On the response of the Antarctic Circumpolar Current transport to climate change in coupled climate models

The CMIP3 (IPCC AR4) models show a consistent intensification and poleward shift of the westerly winds over the Southern Ocean during the 21st century. However, the responses of the Antarctic Circumpolar Currents (ACC) show great diversity in these models, with many even showing reductions in transport. To obtain some understanding of diverse responses in the ACC transport, we investigate both external atmospheric and internal oceanic processes that control the ACC transport responses in these models. While the strengthened westerlies act to increase the tilt of isopycnal surfaces and hence the ACC transport through Ekman pumping effects, the associated changes in buoyancy forcing generally tend to reduce the surface meridional density gradient. The steepening of isopycnal surfaces induced by increased wind forcing leads to enhanced (parameterized) eddy-induced transports that act to reduce the isopycnal slopes. There is also considerable narrowing of the ACC that tends to reduce the ACC transport, caused mainly by the poleward shifts of the subtropical gyres and to a lesser extent by the equatorward expansions of the subpolar gyres in some models. If the combined effect of these retarding processes is larger than that of enhanced Ekman pumping, the ACC transport will be reduced. In addition, the effect of Ekman pumping on the ACC is reduced in weakly stratified models. These findings give insight into the reliability of IPCC-class model predictions of the Southern Ocean circulation, and into the observed decadal-scale steady ACC transport.

Contact angle of a hemispherical bubble: an analytical approach

We have calculated the equilibrium shape of the axially symmetric Plateau border along which a spherical bubble contacts a flat wall, by analytically integrating Laplace’s equation in the presence of gravity, in the limit of small Plateau border sizes. This method has the advantage that it provides closed-form expressions for the positions and orientations of the Plateau border surfaces. Results are in very good overall agreement with those obtained from a numerical solution procedure, and are consistent with experimental data. In particular we find that the effect of gravity on Plateau border shape is relatively small for typical bubble sizes, leading to a widening of the Plateau border for sessile bubbles and to a narrowing for pendant bubbles. The contact angle of the bubble is found to depend even more weakly on gravity.

A process-based analysis of ocean heat uptake in an AOGCM with an eddy-permitting ocean component

About 90% of the anthropogenic increase in heat stored in the climate system is found the oceans. Therefore it is relevant to understand the details of ocean heat uptake. Here we present a detailed, process-based analysis of ocean heat uptake (OHU) processes in HiGEM1.2, an atmosphere-ocean general circulation model (AOGCM) with an eddy-permitting ocean component of 1/3 degree resolution. Similarly to various other models, HiGEM1.2 shows that the global heat budget is dominated by a downward advection of heat compensated by upward isopycnal diffusion. Only in the upper tropical ocean do we find the classical balance between downward diapycnal diffusion and upward advection of heat. The upward isopycnal diffusion of heat is located mostly in the Southern Ocean, which thus dominates the global heat budget. We compare the responses to a 4xCO2 forcing and an enhancement of the windstress forcing in the Southern Ocean. This highlights the importance of regional processes for the global ocean heat uptake. These are mainly surface fluxes and convection in the high latitudes, and advection in the Southern Ocean mid-latitudes. Changes in diffusion are less important. In line with the CMIP5 models, HiGEM1.2 shows a band of strong OHU in the mid-latitude Southern Ocean in the 4xCO2 run, which is mostly advective. By contrast, in the high-latitude Southern Ocean regions it is the suppression of convection that leads to OHU. In the enhanced windstress run, convection is strengthened at high Southern latitudes, leading to heat loss, while the magnitude of the OHU in the Southern mid-latitudes is very similar to the 4xCO2 results. Remarkably, there is only very small global OHU in the enhanced windstress run. The wind stress forcing just leads to a redistribution of heat. We relate the ocean changes at high southern latitudes to the effect of climate change on the Antarctic Circumpolar Current (ACC). It weakens in the 4xCO2 run and strengthens in the wind stress run. The weakening is due to a narrowing of the ACC, caused by an expansion of the Weddell Gyre, and a flattening of the isopycnals, which are explained by a combination of the wind stress forcing and increased precipitation.

Flanking SNP markers for vicine–convicine concentration in faba bean (Vicia faba L).

The pyrimidine glycosides, vicine and convicine, limit the use of faba bean (Vicia faba L.) as food and feed. A single recessive gene, vc-, is responsible for a lowered vicine–convicine concentration. The biosynthetic pathway of these closely related compounds is not known, and the nearest available markers are several cM away from vc-. Improved markers would assist breeding and help to identify candidate genes. A segregating population of 210 F5 recombinant inbred lines was developed from the cross of Mélodie/2 (low vicine–convicine) × ILB 938/2 (normal vicine–convicine), and vicine–convicine concentrations were determined twice on each line. The population was genotyped with a set of 188 SNPs. A strong, single QTL for vicine–convicine concentration was identified on chromosome I, flanked by markers 1.0 cM away on one side and 2.6 cM on the other. The interval defined by these markers in the model species Medicago truncatula includes about 340 genes, but no candidate genes were identified. Further fine mapping should lead to the identification of tightly linked markers as well as narrowing down the search for candidate regulatory or biosynthetic genes which could underlie the vc- locus.