Tuning thermal properties and microphase separation in aliphatic polyester ABA copolymers

Four alkyl substituted ��-lactones were investigated as monomers in ring opening polymerisation to produce a family of poly(3-hydroxyalkanoate)s. Homopolymers were synthesised using a robust aluminium salen catalyst, resulting in polymers with low dispersity (�� < 1.1) and predictable molecular weights. ABA triblock copolymers were prepared using poly(L-lactic acid) as the A block and the aforementioned poly(3-hydroxyalkanoate) as the B block via a sequential addition method. Characterisation of these copolymers determined they were well controlled with low dispersities and predictable molecular weight. DSC analysis determined copolymers prepared from ��-butyrolactone or ��-valerolactone yielded polymers with tunable and predictable thermal properties. Copolymers prepared from ��-heptanolactone yielded a microphase separated material as indicated by SAXS, with two distinct Tgs. The polymers could be readily cast into flexible films and their improved tensile properties were explored.

The greening of Arabia: multiple opportunities for human occupation of the Arabian peninsula during the Late Pleistocene inferred from an ensemble of climate model simulations

Climate models are potentially useful tools for addressing human dispersals and demographic change. The Arabian Peninsula is becoming increasingly significant in the story of human dispersals out of Africa during the Late Pleistocene. Although characterised largely by arid environments today, emerging climate records indicate that the peninsula was wetter many times in the past, suggesting that the region may have been inhabited considerably more than hitherto thought. Explaining the origins and spatial distribution of increased rainfall is challenging because palaeoenvironmental research in the region is in an early developmental stage. We address environmental oscillations by assembling and analysing an ensemble of five global climate models (CCSM3, COSMOS, HadCM3, KCM, and NorESM). We focus on precipitation, as the variable is key for the development of lakes, rivers and savannas. The climate models generated here were compared with published palaeoenvironmental data such as palaeolakes, speleothems and alluvial fan records as a means of validation. All five models showed, to varying degrees, that the Arabia Peninsula was significantly wetter than today during the Last Interglacial (130 ka and 126/125 ka timeslices), and that the main source of increased rainfall was from the North African summer monsoon rather than the Indian Ocean monsoon or from Mediterranean climate patterns. Where available, 104 ka (MIS 5c), 56 ka (early MIS 3) and 21 ka (LGM) timeslices showed rainfall was present but not as extensive as during the Last Interglacial. The results favour the hypothesis that humans potentially moved out of Africa and into Arabia on multiple occasions during pluvial phases of the Late Pleistocene.

The monetary benefit of early flood warnings in Europe

Effective disaster risk management relies on science-based solutions to close the gap between prevention and preparedness measures. The consultation on the United Nations post-2015 framework for disaster risk reduction highlights the need for cross-border early warning systems to strengthen the preparedness phases of disaster risk management, in order to save lives and property and reduce the overall impact of severe events. Continental and global scale flood forecasting systems provide vital early flood warning information to national and international civil protection authorities, who can use this information to make decisions on how to prepare for upcoming floods. Here the potential monetary benefits of early flood warnings are estimated based on the forecasts of the continental-scale European Flood Awareness System (EFAS) using existing flood damage cost information and calculations of potential avoided flood damages. The benefits are of the order of 400 Euro for every 1 Euro invested. A sensitivity analysis is performed in order to test the uncertainty in the method and develop an envelope of potential monetary benefits of EFAS warnings. The results provide clear evidence that there is likely a substantial monetary benefit in this cross-border continental-scale flood early warning system. This supports the wider drive to implement early warning systems at the continental or global scale to improve our resilience to natural hazards.

Implications of event attribution for loss and damage policy

The United Nations Framework Convention on Climate Change (UNFCCC) has established the Warsaw International Mechanism (WIM) to deal with loss and damage associated with climate change impacts, including extreme events, in developing countries. It is not yet known whether events will need to be attributed to anthropogenic climate change to be considered under the WIM. Attribution is possible for some extreme events- a climate model assessment can estimate how greenhouse gas emissions have affected the likelihood of their occurrence. Dialogue between scientists and stakeholders is required to establish whether, and how, this science could play a role in the WIM.

Advances in understanding mineral dust and boundary layer processes over the Sahara from Fennec aircraft observations

The Fennec climate program aims to improve understanding of the Saharan climate system through a synergy of observations and modelling. We present a description of the Fennec airborne observations during 2011 and 2012 over the remote Sahara (Mauritania and Mali) and the advances in the understanding of mineral dust and boundary layer processes they have provided. Aircraft instrumentation aboard the UK FAAM BAe146 and French SAFIRE Falcon 20 is described, with specific focus on instrumentation specially developed and relevant to Saharan meteorology and dust. Flight locations, aims and associated meteorology are described. Examples and applications of aircraft measurements from the Fennec flights are presented, highlighting new scientific results delivered using a synergy of different instruments and aircraft. These include: (1) the first airborne measurement of dust particles sized up to 300 microns and associated dust fluxes in the Saharan atmospheric boundary layer (SABL), (2) dust uplift from the breakdown of the nocturnal low-level jet before becoming visible in SEVIRI satellite imagery, (3) vertical profiles of the unique vertical structure of turbulent fluxes in the SABL, (4) in-situ observations of processes in SABL clouds showing dust acting as CCN and IN at ���15 ��C, (5) dual-aircraft observations of the SABL dynamics, thermodynamics and composition in the Saharan heat low region (SHL), (6) airborne observations of a dust storm associated with a cold-pool (haboob) issued from deep convection over the Atlas, (7) the first airborne chemical composition measurements of dust in the SHL region with differing composition, sources (determined using Lagrangian backward trajectory calculations) and absorption properties between 2011 and 2012, (8) coincident ozone and dust surface area measurements suggest coarser particles provide a route for ozone depletion, (9) discrepancies between airborne coarse mode size distributions and AERONET sunphotometer retrievals under light dust loadings. These results provide insights into boundary layer and dust processes in the SHL region ��� a region of substantial global climatic importance.

The representation of the West-African Monsoon vertical cloud structure in the Met Office Unified Model: an evaluation with CloudSat

Weather and climate model simulations of the West African Monsoon (WAM) have generally poor representation of the rainfall distribution and monsoon circulation because key processes, such as clouds and convection, are poorly characterized. The vertical distribution of cloud and precipitation during the WAM are evaluated in Met Office Unified Model simulations against CloudSat observations. Simulations were run at 40-km and 12-km horizontal grid length using a convection parameterization scheme and at 12-km, 4-km, and 1.5-km grid length with the convection scheme effectively switched off, to study the impact of model resolution and convection parameterization scheme on the organisation of tropical convection. Radar reflectivity is forward-modelled from the model cloud fields using the CloudSat simulator to present a like-with-like comparison with the CloudSat radar observations. The representation of cloud and precipitation at 12-km horizontal grid length improves dramatically when the convection parameterization is switched off, primarily because of a reduction in daytime (moist) convection. Further improvement is obtained when reducing model grid length to 4 km or 1.5 km, especially in the representation of thin anvil and mid-level cloud, but three issues remain in all model configurations. Firstly, all simulations underestimate the fraction of anvils with cloud top height above 12 km, which can be attributed to too low ice water contents in the model compared to satellite retrievals. Secondly, the model consistently detrains mid-level cloud too close to the freezing level, compared to higher altitudes in CloudSat observations. Finally, there is too much low-level cloud cover in all simulations and this bias was not improved when adjusting the rainfall parameters in the microphysics scheme. To improve model simulations of the WAM, more detailed and in-situ observations of the dynamics and microphysics targeting these non-precipitating cloud types are required.

Quantifying particle size and turbulent scale dependence of dust uplift in the Sahara using aircraft measurements

The first size-resolved airborne measurements of dust fluxes and the first dust flux measurements from the central Sahara are presented and compared with a parameterization by Kok (2011a). High-frequency measurements of dust size distribution were obtained from 0.16 to 300 ��m diameter, and eddy covariance fluxes were derived. This is more than an order of magnitude larger size range than previous flux estimates. Links to surface emission are provided by analysis of particle drift velocities. Number flux is described by a ���2 power law between 1 and 144 ��m diameter, significantly larger than the 12 ��m upper limit suggested by Kok (2011a). For small particles, the deviation from a power law varies with terrain type and the large size cutoff is correlated with atmospheric vertical turbulent kinetic energy, suggesting control by vertical transport rather than emission processes. The measured mass flux mode is in the range 30���100 ��m. The turbulent scales important for dust flux are from 0.1 km to 1���10 km. The upper scale increases during the morning as boundary layer depth and eddy size increase. All locations where large dust fluxes were measured had large topographical variations. These features are often linked with highly erodible surface features, such as wadis or dunes. We also hypothesize that upslope flow and flow separation over such features enhance the dust flux by transporting large particles out of the saltation layer. The tendency to locate surface flux measurements in open, flat terrain means these favored dust sources have been neglected in previous studies.

Sticking to the script? The co-production of Neighbourhood Planning in England

Efforts to engage with communities in spatial planning have been criticised as being tokenistic, vehicles for co-option or designed to promote neo-liberal agendas. The introduction of neighbourhood planning (NP) in England under the Localism Act (2011) is claimed by proponents to be a step change in the way that local communities are involved in planning their own areas. However, little empirical evidence has yet emerged to substantiate such claims, or provide details about the practices and experiences of NP. The paper highlights that there are numerous parties involved in the co-production of Neighbourhood Development Plans and there are numerous instances where ideas, policies and priorities that emerge from within neighbourhoods are being ���rescripted��� to ensure conformity to a bounded form of collaboration.

The interaction of moist convection and mid-level dry air in the advance of the onset of the Indian monsoon

The advance of the onset of the Indian monsoon is here explained in terms of a balance between the low-level monsoon flow and an over-running intrusion of mid-tropospheric dry air. The monsoon advances, over a period of about 6 weeks, from the south of the country to the northwest. Given that the low-level monsoon winds are westerly or southwesterly, and the midlevel winds northwesterly, the monsoon onset propagates upwind relative to midlevel flow, and perpendicular to the low-level flow, and is not directly caused by moisture flux toward the northwest. Lacking a conceptual model for the advance means that it has been hard to understand and correct known biases in weather and climate prediction models. The mid-level northwesterlies form a wedge of dry air that is deep in the far northwest of India and over-runs the monsoon flow. The dry layer is moistened from below by shallow cumulus and congestus clouds, so that the profile becomes much closer to moist adiabatic, and the dry layer is much shallower in the vertical, toward the southeast of India. The profiles associated with this dry air show how the most favourable environment for deep convection occurs in the south, and onset occurs here first. As the onset advances across India, the advection of moisture from the Arabian Sea becomes stronger, and the mid-level dry air is increasingly moistened from below. This increased moistening makes the wedge of dry air shallower throughout its horizontal extent, and forces the northern limit of moist convection to move toward the northwest. Wetting of the land surface by rainfall will further reinforce the north-westward progression, by sustaining the supply of boundary layer moisture and shallow cumulus. The local advance of the monsoon onset is coincident with weakening of the mid-level northwesterlies, and therefore weakened mid-level dry advection.

The take-up of Neighbourhood Planning in England 2011-2015

Exploration of how neighbourhoods and others have responded to the UK government���s localism agenda in England, and specifically towards Neighbourhood Planning (NP), is important given that NP is a prominent part of that policy agenda. It is also of interest as the ramifications emerge for planning practice in the formal introduction of statutory plans which are ostensibly led by communities (Parker et al, 2015; Gallent, 2013). There is a necessary task to provide critical commentary on the socio-economic impact of localist policy. The paper explores the issues arising from experience thus far and highlights the take-up of Neighbourhood Planning since 2011. This assessment shows how a vast majority of those active have been in parished areas and in less-deprived areas. This indicates that government needs to do more to ensure that NP is accessible and worthwhile for a wider range of communities.

Phosphorothioate backbone modifications of nucleotide-based drugs are potent platelet activators

Nucleotide-based drug candidates such as antisense oligonucleotides, aptamers, immunoreceptor-activating nucleotides, or (anti)microRNAs hold great therapeutic promise for many human diseases. Phosphorothioate (PS) backbone modification of nucleotide-based drugs is common practice to protect these promising drug candidates from rapid degradation by plasma and intracellular nucleases. Effects of the changes in physicochemical properties associated with PS modification on platelets have not been elucidated so far. Here we report the unexpected binding of PS-modified oligonucleotides to platelets eliciting strong platelet activation, signaling, reactive oxygen species generation, adhesion, spreading, aggregation, and thrombus formation in vitro and in vivo. Mechanistically, the platelet-specific receptor glycoprotein VI (GPVI) mediates these platelet-activating effects. Notably, platelets from GPVI function-deficient patients do not exhibit binding of PS-modified oligonucleotides, and platelet activation is fully abolished. Our data demonstrate a novel, unexpected, PS backbone-dependent, platelet-activating effect of nucleotide-based drug candidates mediated by GPVI. This unforeseen effect should be considered in the ongoing development programs for the broad range of upcoming and promising DNA/RNA therapeutics.

The role of Planning Aid England in supporting communities��� engagement in planning

In considering the position of community engagement within planning in a time of neo-liberalism and a context of ���neo-communitarian localism��� (cf. Jessop, 2002; DeFilippis, 2004), this paper reviews the role and relevance of Planning Aid in terms of its performance and aspirations in guiding and transforming planning practice (Friedmann, 1973; 1987; 2011) since its inception in 1973. In doing this we reflect on the critiques of Planning Aid performance provided by Allmendinger (2004) and bring the account up-to-date following on from past considerations (e.g. Bidwell and Edgar, 1982; Thomas, 1992; Brownill and Carpenter, 2007a,b; Carpenter and Brownill, 2008) and prompted by the 35 years since the University of Reading produced the first published work reviewing Planning Aid (Curtis and Edwards, 1980). Our paper is timely given renewed attacks on planning, the implementation of a form of localism and reductions in funding for planning in a time of austerity. Our view is that the need for forms of ���neo-advocacy��� planning and community development are perhaps even more necessary now, given the continuing under-representation of lower income groups, minority groups and to allow for the expression of alternative planning futures. Thus further consideration of how to ensure that Planning Aid functions are sustained and understood requires the attention of policymakers and the planning profession more widely.

Understanding inter-satellite biases of microwave humidity sounders using global simultaneous nadir overpasses

Simultaneous nadir overpasses (SNOs) of polar-orbiting satellites are most frequent in polar areas but can occur at any latitude when the equatorial crossing times of the satellites become close owing to orbital drift. We use global SNOs of polar orbiting satellites to evaluate the intercalibration of microwave humidity sounders from the more frequent high-latitude SNOs. We have found based on sensitivity analyses that optimal distance and time thresholds for defining collocations are pixel centers less than 5 km apart and time differences less than 300 s. These stringent collocation criteria reduce the impact of highly variable surface or atmospheric conditions on the estimated biases. Uncertainties in the estimated biases are dominated by the combined radiometric noise of the instrument pair. The effects of frequency changes between different versions of the humidity sounders depend on the amount of water vapor in the atmosphere. There are significant scene radiance and thus latitude dependencies in the estimated biases and this has to taken into account while intercalibrating microwave humidity sounders. Therefore the results obtained using polar SNOs will not be representative for moist regions, necessitating the use of global collocations for reliable intercalibration.

Endothelin-1 and fibroblast growth factors stimulate the mitogen-activated protein kinase signaling cascade in cardiac myocytes. The potential role of the cascade in the integration of two signaling pathways leading to myocyte hypertrophy.

Maximally effective concentrations of endothelin-1 (ET-1), acidic FGF (aFGF), or 12-O-tetradecanoylphorbol-13-acetate (TPA) activated mitogen-activated protein kinase (MAPK) by 3-4-fold in crude extracts of myocytes cultured from neonatal rat heart ventricles. Maximal activation was achieved after 5 min. Thereafter, MAPK activity stimulated by ET-1 or aFGF declined to control values within 1-2 h, whereas activation by TPA was more sustained. Two peaks of MAPK activity (a 42- and a 44-kDa MAPK) were resolved in cells exposed to ET-1 or aFGF by fast protein liquid chromatography on a Mono Q column. One major and one minor peak of MAPK kinase (MAPKK) was stimulated by ET-1 or aFGF. Cardiac myocytes expressed protein kinase C (PKC)-alpha, -delta, -epsilon and -zeta as shown immunoblotting. Exposure to 1 microM TPA for 24 h down-regulated PKC-alpha, -delta, and -epsilon, but not PKC-zeta. This maneuver wholly abolished the activation of MAPK on re-exposure to TPA but did not affect the response to aFGF. The effect of ET-1 was partially down-regulated. ET-1 stimulated phospho[3H]inositide hydrolysis 18-fold, whereas aFGF stimulated by only 30%. Agonists which initially utilize dissimilar signaling pathways may therefore converge at the level of MAPKK/MAPK and this may be relevant to the hypertrophic response of the heart.