Hydrogen-bonding-driven self-assembly of PEGylated organosilica nanoparticles with poly(acrylic acid) in aqueous solutions and in layer-by-layer deposition at solid surfaces

PEGylated organosilica nanoparticles have been synthesized through self-condensation of (3-mercaptopropyl)trimethoxysilane in dimethyl sulfoxide into thiolated nanoparticles with their subsequent reaction with methoxypoly(ethylene glycol) maleimide. The PEGylated nanoparticles showed excellent colloidal stability over a wide range of pH in contrast to the parent thiolated nanoparticles, which have a tendency to aggregate irreversibly under acidic conditions (pH < 3.0). Due to the presence of a poly(ethylene glycol)-based corona, the PEGylated nanoparticles are capable of forming hydrogen-bonded interpolymer complexes with poly(acrylic acid) in aqueous solutions under acidic conditions, resulting in larger aggregates. The use of hydrogen-bonding interactions allows more efficient attachment of the nanoparticles to surfaces. The alternating deposition of PEGylated nanoparticles and poly(acrylic acid) on silicon wafer surfaces in a layer-by-layer fashion leads to multilayered coatings. The self-assembly of PEGylated nanoparticles with poly(acrylic acid) in aqueous solutions and at solid surfaces was compared to the behavior of linear poly(ethylene glycol). The nanoparticle system creates thicker layers than the poly(ethylene glycol), and a thicker layer is obtained on a poly(acrylic acid) surface than on a silica surface, because of the effects of hydrogen bonding. Some implications of these hydrogen-bonding-driven interactions between PEGylated nanoparticles and poly(acrylic acid) for pharmaceutical formulations are discussed.

Wind-driven mixing below the oceanic mixed layer

This study describes the turbulent processes in the upper ocean boundary layer forced by a constant surface stress in the absence of the Coriolis force using large-eddy simulation. The boundary layer that develops has a two-layer structure, a well-mixed layer above a stratified shear layer. The depth of the mixed layer is approximately constant, whereas the depth of the shear layer increases with time. The turbulent momentum flux varies approximately linearly from the surface to the base of the shear layer. There is a maximum in the production of turbulence through shear at the base of the mixed layer. The magnitude of the shear production increases with time. The increase is mainly a result of the increase in the turbulent momentum flux at the base of the mixed layer due to the increase in the depth of the boundary layer. The length scale for the shear turbulence is the boundary layer depth. A simple scaling is proposed for the magnitude of the shear production that depends on the surface forcing and the average mixed layer current. The scaling can be interpreted in terms of the divergence of a mean kinetic energy flux. A simple bulk model of the boundary layer is developed to obtain equations describing the variation of the mixed layer and boundary layer depths with time. The model shows that the rate at which the boundary layer deepens does not depend on the stratification of the thermocline. The bulk model shows that the variation in the mixed layer depth is small as long as the surface buoyancy flux is small.

Passive urban ventilation by combined buoyancy-driven slope flow and wall flow: Parametric CFD studies on idealized city models

This paper reports the results of a parametric CFD study on idealized city models to investigate the potential of slope flow in ventilating a city located in a mountainous region when the background synoptic wind is absent. Examples of such a city include Tokyo in Japan, Los Angeles and Phoenix in the US, and Hong Kong. Two types of buoyancy-driven flow are considered, i.e., slope flow from the mountain slope (katabatic wind at night and anabatic wind in the daytime), and wall flow due to heated/cooled urban surfaces. The combined buoyancy-driven flow system can serve the purpose of dispersing the accumulated urban air pollutants when the background wind is weak or absent. The microscopic picture of ventilation performance within the urban structures was evaluated in terms of air change rate (ACH) and age of air. The simulation results reveal that the slope flow plays an important role in ventilating the urban area, especially in calm conditions. Katabatic flow at night is conducive to mitigating the nocturnal urban heat island. In the present parametric study, the mountain slope angle and mountain height are assumed to be constant, and the changing variables are heating/cooling intensity and building height. For a typical mountain of 500 m inclined at an angle of 20° to the horizontal level, the interactive structure is very much dependent on the ratio of heating/cooling intensity as well as building height. When the building is lower than 60 m, the slope wind dominates. When the building is as high as 100 m, the contribution from the urban wall flow cannot be ignored. It is found that katabatic wind can be very beneficial to the thermal environment as well as air quality at the pedestrian level. The air change rate for the pedestrian volume can be as high as 300 ACH.

NGOs, elite capture and community-driven development: perspectives in rural Mozambique

This article examines the problems of elite capture in community driven development (CDD). Drawing on two case studies of non-governmental organisation (NGO) intervention in rural Mozambique, the authors consider two important variables – 1) the diverse and complex contributions of local elites to CDD in different locations, and 2) the roles that non-elites play in monitoring and controlling leader activities – to argue that donors should be cautious about automatically assuming the prevalence of malevolent patrimonialism and its ill-effects in their projects. This is because the ‘checks and balances’ on elite behaviour that exist within locally-defined and historically-rooted forms of community-based governance are likely to be more effective than those introduced by the external intervener.

Predicting natural ventilation in a two-zone building driven by combined forces.

Natural ventilation relies on less controllable natural forces so that it needs more artificial control, and thus its prediction, design and analysis become more important. This paper presents both theoretical and numerical simulations for predicting the natural ventilation flow in a two-zone building with multiple openings which is subjected to the combined natural forces. To our knowledge, this is the first analytical solutions obtained so far for a building with more than one zones and in each zone with possibly more than 2 openings. The analytical solution offers a possibility for validating a multi-zone airflow program. A computer program MIX is employed to conduct the numerical simulation. Good agreement is achieved. Different airflow modes are identified and some design recommendations are also provided.

A feasible study of EEG-driven assistive robotic system for stroke rehabilitation

Stroke is a medical emergency and can cause a neurological damage, affecting the motor and sensory systems. Harnessing brain plasticity should make it possible to reconstruct the closed loop between the brain and the body, i.e., association of the generation of the motor command with the somatic sensory feedback might enhance motor recovery. In order to aid reconstruction of this loop with a robotic device it is necessary to assist the paretic side of the body at the right moment to achieve simultaneity between motor command and feedback signal to somatic sensory area in brain. To this end, we propose an integrated EEG-driven assistive robotic system for stroke rehabilitation. Depending on the level of motor recovery, it is important to provide adequate stimulation for upper limb motion. Thus, we propose an assist arm incorporating a Magnetic Levitation Joint that can generate a compliant motion due to its levitation and mechanical redundancy. This paper reports on a feasibility study carried out to verify the validity of the robot sensing and on EEG measurements conducted with healthy volunteers while performing a spontaneous arm flexion/extension movement. A characteristic feature was found in the temporal evolution of EEG signal in the single motion prior to executed motion which can aid in coordinating timing of the robotic arm assistance onset.

Space weather driven changes in lower atmosphere phenomena

During a period of heliospheric disturbance in 2007-9 associated with a co-rotating interaction region (CIR), a characteristic periodic variation becomes apparent in neutron monitor data. This variation is phase locked to periodic heliospheric current sheet crossings. Phase-locked electrical variations are also seen in the terrestrial lower atmosphere in the southern UK, including an increase in the vertical conduction current density of fair weather atmospheric electricity during increases in the neutron monitor count rate and energetic proton count rates measured by spacecraft. At the same time as the conduction current increases, changes in the cloud microphysical properties lead to an increase in the detected height of the cloud base at Lerwick Observatory, Shetland, with associated changes in surface meteorological quantities. As electrification is expected at the base of layer clouds, which can influence droplet properties, these observations of phase-locked thermodynamic, cloud, atmospheric electricity and solar sector changes are not inconsistent with a heliospheric disturbance driving lower troposphere changes.

Modeling requirement driven architecture of adaptive healthcare system based on semiotics

In order to improve the quality of healthcare services, the integrated large-scale medical information system is needed to adapt to the changing medical environment. In this paper, we propose a requirement driven architecture of healthcare information system with hierarchical architecture. The system operates through the mapping mechanism between these layers and thus can organize functions dynamically adapting to user’s requirement. Furthermore, we introduce the organizational semiotics methods to capture and analyze user’s requirement through ontology chart and norms. Based on these results, the structure of user’s requirement pattern (URP) is established as the driven factor of our system. Our research makes a contribution to design architecture of healthcare system which can adapt to the changing medical environment.

Scenario and modelling uncertainty in global mean temperature change derived from emission-driven global climate models

We compare future changes in global mean temperature in response to different future scenarios which, for the first time, arise from emission-driven rather than concentration-driven perturbed parameter ensemble of a global climate model (GCM). These new GCM simulations sample uncertainties in atmospheric feedbacks, land carbon cycle, ocean physics and aerosol sulphur cycle processes. We find broader ranges of projected temperature responses arising when considering emission rather than concentration-driven simulations (with 10–90th percentile ranges of 1.7 K for the aggressive mitigation scenario, up to 3.9 K for the high-end, business as usual scenario). A small minority of simulations resulting from combinations of strong atmospheric feedbacks and carbon cycle responses show temperature increases in excess of 9 K (RCP8.5) and even under aggressive mitigation (RCP2.6) temperatures in excess of 4 K. While the simulations point to much larger temperature ranges for emission-driven experiments, they do not change existing expectations (based on previous concentration-driven experiments) on the timescales over which different sources of uncertainty are important. The new simulations sample a range of future atmospheric concentrations for each emission scenario. Both in the case of SRES A1B and the Representative Concentration Pathways (RCPs), the concentration scenarios used to drive GCM ensembles, lies towards the lower end of our simulated distribution. This design decision (a legacy of previous assessments) is likely to lead concentration-driven experiments to under-sample strong feedback responses in future projections. Our ensemble of emission-driven simulations span the global temperature response of the CMIP5 emission-driven simulations, except at the low end. Combinations of low climate sensitivity and low carbon cycle feedbacks lead to a number of CMIP5 responses to lie below our ensemble range. The ensemble simulates a number of high-end responses which lie above the CMIP5 carbon cycle range. These high-end simulations can be linked to sampling a number of stronger carbon cycle feedbacks and to sampling climate sensitivities above 4.5 K. This latter aspect highlights the priority in identifying real-world climate-sensitivity constraints which, if achieved, would lead to reductions on the upper bound of projected global mean temperature change. The ensembles of simulations presented here provides a framework to explore relationships between present-day observables and future changes, while the large spread of future-projected changes highlights the ongoing need for such work.

A statistical model for sea surface diurnal warming driven by numercial weather predictions fluxes and winds

A statistical model is derived relating the diurnal variation of sea surface temperature (SST) to the net surface heat flux and surface wind speed from a numerical weather prediction (NWP) model. The model is derived using fluxes and winds from the European Centre for Medium-Range Weather Forecasting (ECMWF) NWP model and SSTs from the Spinning Enhanced Visible and Infrared Imager (SEVIRI). In the model, diurnal warming has a linear dependence on the net surface heat flux integrated since (approximately) dawn and an inverse quadratic dependence on the maximum of the surface wind speed in the same period. The model coefficients are found by matching, for a given integrated heat flux, the frequency distributions of the maximum wind speed and the observed warming. Diurnal cooling, where it occurs, is modelled as proportional to the integrated heat flux divided by the heat capacity of the seasonal mixed layer. The model reproduces the statistics (mean, standard deviation, and 95-percentile) of the diurnal variation of SST seen by SEVIRI and reproduces the geographical pattern of mean warming seen by the Advanced Microwave Scanning Radiometer (AMSR-E). We use the functional dependencies in the statistical model to test the behaviour of two physical model of diurnal warming that display contrasting systematic errors.

A benchmark-driven modelling approach for evaluating deployment choices on a multicore architecture

The complexity of current and emerging high performance architectures provides users with options about how best to use the available resources, but makes predicting performance challenging. In this work a benchmark-driven performance modelling approach is outlined that is appro- priate for modern multicore architectures. The approach is demonstrated by constructing a model of a simple shallow water code on a Cray XE6 system, from application-specific benchmarks that illustrate precisely how architectural char- acteristics impact performance. The model is found to recre- ate observed scaling behaviour up to 16K cores, and used to predict optimal rank-core affinity strategies, exemplifying the type of problem such a model can be used for.

Eddy-driven exchange between the open ocean and a sub-ice shelf cavity

The exchange between the open ocean and sub-ice shelf cavities is important to both water mass transformations and ice shelf melting. Here we use a high-resolution (500 m) numerical model to investigate to which degree eddies produced by frontal instability at the edge of a polynya are capable of transporting dense High Salinity Shelf Water (HSSW) underneath an ice shelf. The applied surface buoyancy flux and ice shelf geometry is based on Ronne Ice Shelf in the southern Weddell Sea, an area of intense wintertime sea ice production where a flow of HSSW into the cavity has been observed. Results show that eddies are able to enter the cavity at the southwestern corner of the polynya where an anticyclonic rim current intersects the ice shelf front. The size and time scale of simulated eddies are in agreement with observations close to the Ronne Ice Front. The properties and strength of the inflow are sensitive to the prescribed total ice production, flushing the ice shelf cavity at a rate of 0.2–0.4 × 106 m3 s−1 depending on polynya size and magnitude of surface buoyancy flux. Eddy-driven HSSW transport into the cavity is reduced by about 50% if the model grid resolution is decreased to 2-5 km and eddies are not properly resolved.

Generation of a buoyancy-driven coastal current by an Antarctic Polynya

Descent and spreading of high salinity water generated by salt rejection during sea ice formation in an Antarctic coastal polynya is studied using a hydrostatic, primitive equation three-dimensional ocean model called the Proudman Oceanographic Laboratory Coastal Ocean Modeling System (POLCOMS). The shape of the polynya is assumed to be a rectangle 100 km long and 30 km wide, and the salinity flux into the polynya at its surface is constant. The model has been run at high horizontal spatial resolution (500 m), and numerical simulations reveal a buoyancy-driven coastal current. The coastal current is a robust feature and appears in a range of simulations designed to investigate the influence of a sloping bottom, variable bottom drag, variable vertical turbulent diffusivities, higher salinity flux, and an offshore position of the polynya. It is shown that bottom drag is the main factor determining the current width. This coastal current has not been produced with other numerical models of polynyas, which may be because these models were run at coarser resolutions. The coastal current becomes unstable upstream of its front when the polynya is adjacent to the coast. When the polynya is situated offshore, an unstable current is produced from its outset owing to the capture of cyclonic eddies. The effect of a coastal protrusion and a canyon on the current motion is investigated. In particular, due to the convex shape of the coastal protrusion, the current sheds a dipolar eddy.

Experimentally driven atomistic model of 1,2 Polybutadiene

We present an efficient method of combining wide angle neutron scattering data with detailed atomistic models, allowing us to perform a quantitative and qualitative mapping of the organisation of the chain conformation in both glass and liquid phases. The structural refinement method presented in this work is based on the exploitation of the intrachain features of the diffraction pattern and its intimate linkage with atomistic models by the use of internal coordinates for bond lengths, valence angles and torsion rotations. Atomic connectivity is defined through these coordinates that are in turn assigned by pre-defined probability distributions, thus allowing for the models in question to be built stochastically. Incremental variation of these coordinates allows for the construction of models that minimise the differences between the observed and calculated structure factors. We present a series of neutron scattering data of 1,2 polybutadiene at the region 120-400K. Analysis of the experimental data yield bond lengths for C-C and C=C of 1.54Å and 1.35Å respectively. Valence angles of the backbone were found to be at 112° and the torsion distributions are characterised by five rotational states, a three-fold trans-skew± for the backbone and gauche± for the vinyl group. Rotational states of the vinyl group were found to be equally populated, indicating a largely atactic chan. The two backbone torsion angles exhibit different behaviour with respect to temperature of their trans population, with one of them adopting an almost all trans sequence. Consequently the resulting configuration leads to a rather persistent chain, something indicated by the value of the characteristic ratio extrapolated from the model. We compare our results with theoretical predictions, computer simulations, RIS models and previously reported experimental results.

Climate-driven spatial mismatches between British orchards and their pollinators: increased risks of pollination deficits

Understanding how climate change can affect crop-pollinator systems helps predict potential geographical mismatches between a crop and its pollinators, and therefore identify areas vulnerable to loss of pollination services. We examined the distribution of orchard species (apples, pears, plums and other top fruits) and their pollinators in Great Britain, for present and future climatic conditions projected for 2050 under the SRES A1B Emissions Scenario. We used a relative index of pollinator availability as a proxy for pollination service. At present there is a large spatial overlap between orchards and their pollinators, but predictions for 2050 revealed that the most suitable areas for orchards corresponded to low pollinator availability. However, we found that pollinator availability may persist in areas currently used for fruit production, but which are predicted to provide sub-optimal environmental suitability for orchard species in the future. Our results may be used to identify mitigation options to safeguard orchard production against the risk of pollination failure in Great Britain over the next 50 years; for instance choosing fruit tree varieties that are adapted to future climatic conditions, or boosting wild pollinators through improving landscape resources. Our approach can be readily applied to other regions and crop systems, and expanded to include different climatic scenarios.