Low-molecular-weight gelators: Elucidating the principles of gelation based on gelator solubility and a cooperative self-assembly model

This paper highlights the key role played by solubility in influencing gelation and demonstrates that many facets of the gelation process depend on this vital parameter. In particular, we relate thermal stability (T-gel) and minimum gelation concentration (MGC) values of small-molecule gelation in terms of the solubility and cooperative self-assembly of gelator building blocks. By employing a van't Hoff analysis of solubility data, determined from simple NMR measurements, we are able to generate T-calc values that reflect the calculated temperature for complete solubilization of the networked gelator. The concentration dependence of T-calc allows the previously difficult to rationalize "plateau-region" thermal stability values to be elucidated in terms of gelator molecular design. This is demonstrated for a family of four gelators with lysine units attached to each end of an aliphatic diamine, with different peripheral groups (Z or Bee) in different locations on the periphery of the molecule. By tuning the peripheral protecting groups of the gelators, the solubility of the system is modified, which in turn controls the saturation point of the system and hence controls the concentration at which network formation takes place. We report that the critical concentration (C-crit) of gelator incorporated into the solid-phase sample-spanning network within the gel is invariant of gelator structural design. However, because some systems have higher solubilities, they are less effective gelators and require the application of higher total concentrations to achieve gelation, hence shedding light on the role of the MGC parameter in gelation. Furthermore, gelator structural design also modulates the level of cooperative self-assembly through solubility effects, as determined by applying a cooperative binding model to NMR data. Finally, the effect of gelator chemical design on the spatial organization of the networked gelator was probed by small-angle neutron and X-ray scattering (SANS/SAXS) on the native gel, and a tentative self-assembly model was proposed.

Performance of phase change material boards under natural convection

The high thermal storage capacity of phase change material (PCM) can reduce energy consumption in buildings through energy storage and release when combined with renewable energy sources, night cooling, etc. PCM boards can be used to absorb heat gains during daytime and release heat at night. In this paper, the thermal performance of an environmental chamber fitted with phase change material boards has been investigated. During a full-cycle experiment, i.e. charging–releasing cycle, the PCM boards on a wall can reduce the interior wall surface temperature during the charging process, whereas the PCM wall surface temperature is higher than that of the other walls during the heat releasing process. It is found that the heat flux density of the PCM wall in the melting zone is almost twice as large as that of ordinary wall. Also, the heat-insulation performance of a PCM wall is better than that of an ordinary wall during the charging process, while during the heat discharging process, the PCM wall releases more heat energy. The convective heat transfer coefficient of PCM wall surface calculated using equations for a normal wall material produces an underestimation of this coefficient. The high convective heat transfer coefficient for a PCM wall is due to the increased energy exchange between the wall and indoor air.

A new theory of educational change - punctuated equilibrium: the case of the internationalisation of Higher Education institutions

This article argues for a new theoretical paradigm for the analysis of change in educational institutions that is able to deal with such issues as readiness for change, transformational change and the failure of change strategies. Punctuated equilibrium (Tushman and Romanelli, 1985) is a theory which has wide application. It envisages long-term change as being made up of a succession of long periods of relative stability interspersed by brief periods of rapid profound change. In the periods of stability only relatively small incremental changes are possible. The periods of transformational change may be triggered by external or internal influences. A recent study of the long-term process of internationalisation in higher education institutions shows evidence to support the theory: long periods of incremental change, events precipitating profound change and the failure of externally imposed attempts to change. Also, as the theory predicts, changes in collegial organisations are slower and more uncertain than changes in managed organisations.

Thermodynamics of climate change: generalized sensitivities

Using a recent theoretical approach, we study how global warming impacts the thermodynamics of the climate system by performing experiments with a simplified yet Earth-like climate model. The intensity of the Lorenz energy cycle, the Carnot efficiency, the material entropy production, and the degree of irreversibility of the system change monotonically with the CO2 concentration. Moreover, these quantities feature an approximately linear behaviour with respect to the logarithm of the CO2 concentration in a relatively wide range. These generalized sensitivities suggest that the climate becomes less efficient, more irreversible, and features higher entropy production as it becomes warmer, with changes in the latent heat fluxes playing a predominant role. These results may be of help for explaining recent findings obtained with state of the art climate models regarding how increases in CO2 concentration impact the vertical stratification of the tropical and extratropical atmosphere and the position of the storm tracks.

A moving-mesh finite element method and its application to the numerical solution of phase-change problems

A distributed Lagrangian moving-mesh finite element method is applied to problems involving changes of phase. The algorithm uses a distributed conservation principle to determine nodal mesh velocities, which are then used to move the nodes. The nodal values are obtained from an ALE (Arbitrary Lagrangian-Eulerian) equation, which represents a generalization of the original algorithm presented in Applied Numerical Mathematics, 54:450--469 (2005). Having described the details of the generalized algorithm it is validated on two test cases from the original paper and is then applied to one-phase and, for the first time, two-phase Stefan problems in one and two space dimensions, paying particular attention to the implementation of the interface boundary conditions. Results are presented to demonstrate the accuracy and the effectiveness of the method, including comparisons against analytical solutions where available.

Bioclimatic envelope model of climate change impacts on blanket peatland distribution in Great Britain

Blanket peatlands are rain-fed mires that cover the landscape almost regardless of topography. The geographical extent of this type of peatland is highly sensitive to climate. We applied a global process-based bioclimatic envelope model, PeatStash, to predict the distribution of British blanket peatlands. The model captures the present areal extent (Kappa = 0.77) and is highly sensitive to both temperature and precipitation changes. When the model is run using the UKCIP02 climate projections for the time periods 2011–2040, 2041–2070 and 2071–2100, the geographical distribution of blanket peatlands gradually retreats towards the north and the west. In the UKCIP02 high emissions scenario for 2071–2100, the blanket peatland bioclimatic space is ~84% smaller than contemporary conditions (1961–1990); only parts of the west of Scotland remain inside this space. Increasing summer temperature is the main driver of the projected changes in areal extent. Simulations using 7 climate model outputs resulted in generally similar patterns of declining aereal extent of the bioclimatic space, although differing in degree. The results presented in this study should be viewed as a first step towards understanding the trends likely to affect the blanket peatland distribution in Great Britain. The eventual fate of existing blanket peatlands left outside their bioclimatic space remains uncertain.

A comparative analysis of projected impacts of climate change on river runoff from global and catchment-scale hydrological models

We present a comparative analysis of projected impacts of climate change on river runoff from two types of distributed hydrological model, a global hydrological model (GHM) and catchment-scale hydrological models (CHM). Analyses are conducted for six catchments that are global in coverage and feature strong contrasts in spatial scale as well as climatic and development conditions. These include the Liard (Canada), Mekong (SE Asia), Okavango (SW Africa), Rio Grande (Brazil), Xiangu (China) and Harper's Brook (UK). A single GHM (Mac-PDM.09) is applied to all catchments whilst different CHMs are applied for each catchment. The CHMs typically simulate water resources impacts based on a more explicit representation of catchment water resources than that available from the GHM, and the CHMs include river routing. Simulations of average annual runoff, mean monthly runoff and high (Q5) and low (Q95) monthly runoff under baseline (1961-1990) and climate change scenarios are presented. We compare the simulated runoff response of each hydrological model to (1) prescribed increases in global mean temperature from the HadCM3 climate model and (2)a prescribed increase in global-mean temperature of 2oC for seven GCMs to explore response to climate model and structural uncertainty. We find that differences in projected changes of mean annual runoff between the two types of hydrological model can be substantial for a given GCM, and they are generally larger for indicators of high and low flow. However, they are relatively small in comparison to the range of projections across the seven GCMs. Hence, for the six catchments and seven GCMs we considered, climate model structural uncertainty is greater than the uncertainty associated with the type of hydrological model applied. Moreover, shifts in the seasonal cycle of runoff with climate change are presented similarly by both hydrological models, although for some catchments the monthly timing of high and low flows differs.This implies that for studies that seek to quantify and assess the role of climate model uncertainty on catchment-scale runoff, it may be equally as feasible to apply a GHM as it is to apply a CHM, especially when climate modelling uncertainty across the range of available GCMs is as large as it currently is. Whilst the GHM is able to represent the broad climate change signal that is represented by the CHMs, we find, however, that for some catchments there are differences between GHMs and CHMs in mean annual runoff due to differences in potential evaporation estimation methods, in the representation of the seasonality of runoff, and in the magnitude of changes in extreme monthly runoff, all of which have implications for future water management issues.

The implications of climate policy for the impacts of climate change on global water resources

This paper assesses the implications of climate policy for exposure to water resources stresses. It compares a Reference scenario which leads to an increase in global mean temperature of 4oC by the end of the 21st century with a Mitigation scenario which stabilises greenhouse gas concentrations at around 450ppm CO2e and leads to a 2oC increase in 2100. Associated changes in river runoff are simulated using a global hydrological model, for four spatial patterns of change in temperature and rainfall. There is a considerable difference in hydrological change between these four patterns, but the percentages of change avoided at the global scale are relatively robust. By the 2050s, the Mitigation scenario typically avoids between 16 and 30% of the change in runoff under the Reference scenario, and by 2100 it avoids between 43 and 65%. Two different measures of exposure to water resources stress are calculated, based on resources per capita and the ratio of withdrawals to resources. Using the first measure, the Mitigation scenario avoids 8-17% of the impact in 2050 and 20-31% in 2100; with the second measure, the avoided impacts are 5-21% and 15-47% respectively. However, at the same time, the Mitigation scenario also reduces the positive impacts of climate change on water scarcity in other areas. The absolute numbers and locations of people affected by climate change and climate policy vary considerably between the four climate model patterns.

The use of scenarios as the basis for combined assessment of climate change mitigation and adaptation

Scenarios are used to explore the consequences of different adaptation and mitigation strategies under uncertainty. In this paper, two scenarios are used to explore developments with (1) no mitigation leading to an increase of global mean temperature of 4 °C by 2100 and (2) an ambitious mitigation strategy leading to 2 °C increase by 2100. For the second scenario, uncertainties in the climate system imply that a global mean temperature increase of 3 °C or more cannot be ruled out. Our analysis shows that, in many cases, adaptation and mitigation are not trade-offs but supplements. For example, the number of people exposed to increased water resource stress due to climate change can be substantially reduced in the mitigation scenario, but adaptation will still be required for the remaining large numbers of people exposed to increased stress. Another example is sea level rise, for which, from a global and purely monetary perspective, adaptation (up to 2100) seems more effective than mitigation. From the perspective of poorer and small island countries, however, stringent mitigation is necessary to keep risks at manageable levels. For agriculture, only a scenario based on a combination of adaptation and mitigation is able to avoid serious climate change impacts.