Time-resolved gas-phase kinetic, quantum chemical, and RRKM studies of reactions of silylene with alcohols

Time-resolved kinetic studies of silylene, SiH2, generated by laser flash photolysis of 1-silacyclopent-3-ene and phenylsilane, have been carried out to obtain rate constants for its bimolecular reactions with methanol, ethanol, 1-propanol, 1-butanol and 2-methyl-1-butanol. The reactions were studied in the gas phase over the pressure range 1-100 Torr in SF6 bath gas, at room temperature. In the study with methanol several buffer gases were used. All five reactions showed pressure dependences characteristic of third body assisted association reactions. The rate constant pressure dependences were modelled using RRKM theory, based on Eo values of the association complexes obtained by ab initio calculation (G3 level). Transition state models were adjusted to fit experimental fall-off curves and extrapolated to obtain k∞ values in the range 1.9 to 4.5 × 10-10 cm3 molecule-1 s-1. These numbers, corresponding to the true bimolecular rate constants, indicate efficiencies of between 16 and 67% of the collision rates for these reactions. In the reaction of SiH2 + MeOH there is a small kinetic component to the rate which is second order in MeOH (at low total pressures). This suggests an additional catalysed reaction pathway, which is supported by the ab initio calculations. These calculations have been used to define specific MeOH-for-H2O substitution effects on this catalytic pathway. Where possible our experimental and theoretical results are compared with those of previous studies.

Graph-based algorithms for comparison and prediction of household-level energy use profiles

We present an efficient graph-based algorithm for quantifying the similarity of household-level energy use profiles, using a notion of similarity that allows for small time–shifts when comparing profiles. Experimental results on a real smart meter data set demonstrate that in cases of practical interest our technique is far faster than the existing method for computing the same similarity measure. Having a fast algorithm for measuring profile similarity improves the efficiency of tasks such as clustering of customers and cross-validation of forecasting methods using historical data. Furthermore, we apply a generalisation of our algorithm to produce substantially better household-level energy use forecasts from historical smart meter data.

FAMOUS, faster: using parallel computing techniques to accelerate the FAMOUS/HadCM3 climate model with a focus on the radiative transfer algorithm

We have optimised the atmospheric radiation algorithm of the FAMOUS climate model on several hardware platforms. The optimisation involved translating the Fortran code to C and restructuring the algorithm around the computation of a single air column. Instead of the existing MPI-based domain decomposition, we used a task queue and a thread pool to schedule the computation of individual columns on the available processors. Finally, four air columns are packed together in a single data structure and computed simultaneously using Single Instruction Multiple Data operations. The modified algorithm runs more than 50 times faster on the CELL’s Synergistic Processing Elements than on its main PowerPC processing element. On Intel-compatible processors, the new radiation code runs 4 times faster. On the tested graphics processor, using OpenCL, we find a speed-up of more than 2.5 times as compared to the original code on the main CPU. Because the radiation code takes more than 60% of the total CPU time, FAMOUS executes more than twice as fast. Our version of the algorithm returns bit-wise identical results, which demonstrates the robustness of our approach. We estimate that this project required around two and a half man-years of work.

Which of satellite- or model-based estimates is closer to reality for aerosol indirect forcing?

In their contribution to PNAS, Penner et al. (1) used a climate model to estimate the radiative forcing by the aerosol first indirect effect (cloud albedo effect) in two different ways: first, by deriving a statistical relationship between the logarithm of cloud droplet number concentration, ln Nc, and the logarithm of aerosol optical depth, ln AOD (or the logarithm of the aerosol index, ln AI) for present-day and preindustrial aerosol fields, a method that was applied earlier to satellite data (2), and, second, by computing the radiative flux perturbation between two simulations with and without anthropogenic aerosol sources. They find a radiative forcing that is a factor of 3 lower in the former approach than in the latter [as Penner et al. (1) correctly noted, only their “inline” results are useful for the comparison]. This study is a very interesting contribution, but we believe it deserves several clarifications.

Flow synthesis using gaseous ammonia in a Teflon AF-2400 tube-in-tube reactor: Paal–Knorr pyrrole formation and gas concentration measurement by inline flow titration

Using a simple and accessible Teflon AF-2400 based tube-intube reactor, a series of pyrroles were synthesised in flow using the Paal–Knorr reaction of 1,4-diketones with gaseous ammonia. An inline flow titration technique allowed measurement of the ammonia concentration and its relationship to residence time and temperature.

The dynamics and measurement of commercial property depreciation in the UK

Beginning with an extensive literature review, this new research summary report analyses the process of rental depreciation, its effect on the performance of rents, and the impacts of capital expenditure on depreciation. It is based on an analysis of more than 700 commercial and industrial properties and newer property types and it is the most comprehensive national study of rental depreciation since the 1986 CALUS report. The report will be of interest to valuers, fund managers, institutional investors and their advisors and researchers.

Computing Fresnel integrals via modified trapezium rules

In this paper we propose methods for computing Fresnel integrals based on truncated trapezium rule approximations to integrals on the real line, these trapezium rules modified to take into account poles of the integrand near the real axis. Our starting point is a method for computation of the error function of complex argument due to Matta and Reichel (J Math Phys 34:298–307, 1956) and Hunter and Regan (Math Comp 26:539–541, 1972). We construct approximations which we prove are exponentially convergent as a function of N , the number of quadrature points, obtaining explicit error bounds which show that accuracies of 10−15 uniformly on the real line are achieved with N=12 , this confirmed by computations. The approximations we obtain are attractive, additionally, in that they maintain small relative errors for small and large argument, are analytic on the real axis (echoing the analyticity of the Fresnel integrals), and are straightforward to implement.

Categorizing users in behavior change support systems based on cognitive dissonance

Most developers of behavior change support systems (BCSS) employ ad hoc procedures in their designs. This paper presents a novel discussion concerning how analyzing the relationship between attitude toward target behavior, current behavior, and attitude toward change or maintaining behavior can facilitate the design of BCSS. We describe the three-dimensional relationships between attitude and behavior (3D-RAB) model and demonstrate how it can be used to categorize users, based on variations in levels of cognitive dissonance. The proposed model seeks to provide a method for analyzing the user context on the persuasive systems design model, and it is evaluated using existing BCSS. We identified that although designers seem to address the various cognitive states, this is not done purposefully, or in a methodical fashion, which implies that many existing applications are targeting users not considered at the design phase. As a result of this work, it is suggested that designers apply the 3D-RAB model in order to design solutions for targeted users.

Towards the computer-aided diagnosis of dementia based on the geometric and network connectivity of structural MRI data

We present an intuitive geometric approach for analysing the structure and fragility of T1-weighted structural MRI scans of human brains. Apart from computing characteristics like the surface area and volume of regions of the brain that consist of highly active voxels, we also employ Network Theory in order to test how close these regions are to breaking apart. This analysis is used in an attempt to automatically classify subjects into three categories: Alzheimer’s disease, mild cognitive impairment and healthy controls, for the CADDementia Challenge.

Heuristic based evolution for the coordination of autonomous vehicles in the absence of speed lanes

The current state of the art in the planning and coordination of autonomous vehicles is based upon the presence of speed lanes. In a traffic scenario where there is a large diversity between vehicles the removal of speed lanes can generate a significantly higher traffic bandwidth. Vehicle navigation in such unorganized traffic is considered. An evolutionary based trajectory planning technique has the advantages of making driving efficient and safe, however it also has to surpass the hurdle of computational cost. In this paper, we propose a real time genetic algorithm with Bezier curves for trajectory planning. The main contribution is the integration of vehicle following and overtaking behaviour for general traffic as heuristics for the coordination between vehicles. The resultant coordination strategy is fast and near-optimal. As the vehicles move, uncertainties may arise which are constantly adapted to, and may even lead to either the cancellation of an overtaking procedure or the initiation of one. Higher level planning is performed by Dijkstra's algorithm which indicates the route to be followed by the vehicle in a road network. Re-planning is carried out when a road blockage or obstacle is detected. Experimental results confirm the success of the algorithm subject to optimal high and low-level planning, re-planning and overtaking.

The interdependence of continental warm cloud properties derived from unexploited solar background signals in ground-based lidar measurements

We have extensively analysed the interdependence between cloud optical depth, droplet effective radius, liquid water path (LWP) and geometric thickness for stratiform warm clouds using ground-based observations. In particular, this analysis uses cloud optical depths retrieved from untapped solar background signals that are previously unwanted and need to be removed in most lidar applications. Combining these new optical depth retrievals with radar and microwave observations at the Atmospheric Radiation Measurement (ARM) Climate Research Facility in Oklahoma during 2005–2007, we have found that LWP and geometric thickness increase and follow a power-law relationship with cloud optical depth regardless of the presence of drizzle; LWP and geometric thickness in drizzling clouds can be generally 20–40 % and at least 10 % higher than those in non-drizzling clouds, respectively. In contrast, droplet effective radius shows a negative correlation with optical depth in drizzling clouds and a positive correlation in non-drizzling clouds, where, for large optical depths, it asymptotes to 10 μm. This asymptotic behaviour in non-drizzling clouds is found in both the droplet effective radius and optical depth, making it possible to use simple thresholds of optical depth, droplet size, or a combination of these two variables for drizzle delineation. This paper demonstrates a new way to enhance ground-based cloud observations and drizzle delineations using existing lidar networks.

A novel ensemble method for retrieving properties of warm cloud in 3-D using ground-based scanning radar and zenith radiances

We present a novel method for retrieving high-resolution, three-dimensional (3-D) nonprecipitating cloud fields in both overcast and broken-cloud situations. The method uses scanning cloud radar and multiwavelength zenith radiances to obtain gridded 3-D liquid water content (LWC) and effective radius (re) and 2-D column mean droplet number concentration (Nd). By using an adaption of the ensemble Kalman filter, radiances are used to constrain the optical properties of the clouds using a forward model that employs full 3-D radiative transfer while also providing full error statistics given the uncertainty in the observations. To evaluate the new method, we first perform retrievals using synthetic measurements from a challenging cumulus cloud field produced by a large-eddy simulation snapshot. Uncertainty due to measurement error in overhead clouds is estimated at 20% in LWC and 6% in re, but the true error can be greater due to uncertainties in the assumed droplet size distribution and radiative transfer. Over the entire domain, LWC and re are retrieved with average error 0.05–0.08 g m-3 and ~2 μm, respectively, depending on the number of radiance channels used. The method is then evaluated using real data from the Atmospheric Radiation Measurement program Mobile Facility at the Azores. Two case studies are considered, one stratocumulus and one cumulus. Where available, the liquid water path retrieved directly above the observation site was found to be in good agreement with independent values obtained from microwave radiometer measurements, with an error of 20 g m-2.

The MELODIES project: integrating diverse data using Linked Data and cloud computing

We present an overview of the MELODIES project, which is developing new data-intensive environmental services based on data from Earth Observation satellites, government databases, national and European agencies and more. We focus here on the capabilities and benefits of the project’s “technical platform”, which applies cloud computing and Linked Data technologies to enable the development of these services, providing flexibility and scalability.

Case study on the maintenance of a construction monitoring using USN-based data acquisition

In recent years, there has been an increasing interest in the adoption of emerging ubiquitous sensor network (USN) technologies for instrumentation within a variety of sustainability systems. USN is emerging as a sensing paradigm that is being newly considered by the sustainability management field as an alternative to traditional tethered monitoring systems. Researchers have been discovering that USN is an exciting technology that should not be viewed simply as a substitute for traditional tethered monitoring systems. In this study, we investigate how a movement monitoring measurement system of a complex building is developed as a research environment for USN and related decision-supportive technologies. To address the apparent danger of building movement, agent-mediated communication concepts have been designed to autonomously manage large volumes of exchanged information. In this study, we additionally detail the design of the proposed system, including its principles, data processing algorithms, system architecture, and user interface specifics. Results of the test and case study demonstrate the effectiveness of the USN-based data acquisition system for real-time monitoring of movement operations.

Subdiffraction fluorescence imaging of biomolecular structure and distributions with quantum dots

We introduce semiconductor quantum dot-based fluorescence imaging with approximately 2-fold increased optical resolution in three dimensions as a method that allows both studying cellular structures and spatial organization of biomolecules in membranes and subcellular organelles. Target biomolecules are labelled with quantum dots via immunocytochemistry. The resolution enhancement is achieved by three-photon absorption of quantum dots and subsequent fluorescence emission from a higher-order excitonic state. Different from conventional multiphoton microscopy, this approach can be realized on any confocal microscope without the need for pulsed excitation light. We demonstrate quantum dot triexciton imaging (QDTI) of the microtubule network of U373 cells, 3D imaging of TNF receptor 2 on the plasma membrane of HeLa cells, and multicolor 3D imaging of mitochondrial cytochrome c oxidase and actin in COS-7 cells.