The effect of the spacer length on the nature of coupling in side chain liquid crystals polymers and elastomers

Side chain liquid crystal polymers and elastomers exhibit a rich phase behaviour which arises from the antagonistic influences of the entropically disordered polymer chain configuration and the long range orientational ordering of the mesogenic units. This competition arises since the natural macroscopic phase separation is inhibited by the inherent chemical connectivity of the system. At the heart of this connectivity is the spacer link and we consider here its influence on the phase behaviour. In particular we consider a series of elastomers in which the number of alkyl units in the spacer is systematically varied from 2 to 6. The lengthening of the coupling spacer is accompanied by an alternation of the sign of coupling between the polymer chain and the mesogenic unit. These results demonstrate the dominating influence of the so-called hinge effect in determining the phase behaviour. In addition to the alternation of the sign there is some decrease in the magnitude of the coupling with increasing spacer length.

The dependence of contrail formation on the weather pattern and altitude in the North Atlantic

Aircraft flying through cold ice-supersaturated air produce persistent contrails which contribute to the climate impact of aviation. Here, we demonstrate the importance of the weather situation, together with the route and altitude of the aircraft through this, on estimating contrail coverage. The results have implications for determining the climate impact of contrails as well as potential mitigation strategies. Twenty-one years of re-analysis data are used to produce a climatological assessment of conditions favorable for persistent contrail formation between 200 and 300 hPa over the north Atlantic in winter. The seasonal-mean frequency of cold ice-supersaturated regions is highest near 300 hPa, and decreases with altitude. The frequency of occurrence of ice-supersaturated regions varies with large-scale weather pattern; the most common locations are over Greenland, on the southern side of the jet stream and around the northern edge of high pressure ridges. Assuming aircraft take a great circle route, as opposed to a more realistic time-optimal route, is likely to lead to an error in the estimated contrail coverage, which can exceed 50% for westbound north Atlantic flights. The probability of contrail formation can increase or decrease with height, depending on the weather pattern, indicating that the generic suggestion that flying higher leads to fewer contrails is not robust.

On the drivers of inter-annual and decadal rainfall variability in Queensland, Australia

Queensland experiences considerable inter-annual and decadal rainfall variability, which impacts water-resource management, agriculture and infrastructure. To understand the mechanisms by which large-scale atmospheric and coupled air–sea processes drive these variations, empirical orthogonal teleconnection (EOT) analysis is applied to 1900–2010 seasonal Queensland rainfall. Fields from observations and the 20th Century Reanalysis are regressed onto the EOT timeseries to associate the EOTs with large-scale drivers. In winter, spring and summer the leading, state-wide EOTs are highly correlated with the El Nino–Southern Oscillation (ENSO); the Inter-decadal Pacific Oscillation modulates the summer ENSO teleconnection. In autumn, the leading EOT is associated with locally driven, late-season monsoon variations, while ENSO affects only tropical northern Queensland. Examining EOTs beyond the first, southeastern Queensland and the Cape York peninsula emerge as regions of coherent rainfall variability. In the southeast, rainfall anomalies respond to the strength and moisture content of onshore easterlies, controlled by Tasman Sea blocking. The summer EOT associated with onshore flow and blocking has been negative since 1970, consistent with the observed decline in rainfall along the heavily populated coast. The southeastern Queensland EOTs show considerable multi-decadal variability, which is independent of large-scale drivers. Summer rainfall in Cape York is associated with tropical-cyclone activity.

Influence of the quasi-biennial oscillation on the extratropical winter stratosphere in an atmospheric general circulation model and in reanalysis data

The interannual variability of the stratospheric polar vortex during winter in both hemispheres is observed to correlate strongly with the phase of the quasi-biennial oscillation (QBO) in tropical stratospheric winds. It follows that the lack of a spontaneously generated QBO in most atmospheric general circulation models (AGCMs) adversely affects the nature of polar variability in such models. This study examines QBO–vortex coupling in an AGCM in which a QBO is spontaneously induced by resolved and parameterized waves. The QBO–vortex coupling in the AGCM compares favorably to that seen in reanalysis data [from the 40-yr ECMWF Re-Analysis (ERA-40)], provided that careful attention is given to the definition of QBO phase. A phase angle representation of the QBO is employed that is based on the two leading empirical orthogonal functions of equatorial zonal wind vertical profiles. This yields a QBO phase that serves as a proxy for the vertical structure of equatorial winds over the whole depth of the stratosphere and thus provides a means of subsampling the data to select QBO phases with similar vertical profiles of equatorial zonal wind. Using this subsampling, it is found that the QBO phase that induces the strongest polar vortex response in early winter differs from that which induces the strongest late-winter vortex response. This is true in both hemispheres and for both the AGCM and ERA-40. It follows that the strength and timing of QBO influence on the vortex may be affected by the partial seasonal synchronization of QBO phase transitions that occurs both in observations and in the model. This provides a mechanism by which changes in the strength of QBO–vortex correlations may exhibit variability on decadal time scales. In the model, such behavior occurs in the absence of external forcings or interannual variations in sea surface temperatures.

On the effect of power amplifier nonlinearity on MIMO transmit diversity systems

Nonlinearity of high-power amplifier (HPA) plays a crucial role in the performance of multiple-input multiple-output (MIMO) systems. In this paper, we investigate the performance of MIMO orthogonal space-time block coding (STBC) systems in the presence of nonlinear HPA. Specifically, we assess the impact of HPA nonlinearity on the average symbol error probability (SEP), total degradation (TD), and system capacity of orthogonal STBC in uncorrelated Nakagami-m fading channels. Numerical results are provided and show the effects of several system parameters, such as the output back-off (OBO) of nonlinear HPA, numbers of transmit and receive antennas, and modulation order of quadrature amplitude modulation (QAM), on performance.

Non-orthogonal version of the arbitrary polygonal C-grid and a new diamond grid

Quasi-uniform grids of the sphere have become popular recently since they avoid parallel scaling bottle- necks associated with the poles of latitude–longitude grids. However quasi-uniform grids of the sphere are often non- orthogonal. A version of the C-grid for arbitrary non- orthogonal grids is presented which gives some of the mimetic properties of the orthogonal C-grid. Exact energy conservation is sacrificed for improved accuracy and the re- sulting scheme numerically conserves energy and potential enstrophy well. The non-orthogonal nature means that the scheme can be used on a cubed sphere. The advantage of the cubed sphere is that it does not admit the computa- tional modes of the hexagonal or triangular C-grids. On var- ious shallow-water test cases, the non-orthogonal scheme on a cubed sphere has accuracy less than or equal to the orthog- onal scheme on an orthogonal hexagonal icosahedron. A new diamond grid is presented consisting of quasi- uniform quadrilaterals which is more nearly orthogonal than the equal-angle cubed sphere but with otherwise similar properties. It performs better than the cubed sphere in ev- ery way and should be used instead in codes which allow a flexible grid structure.

The impact of eBusiness on the City of London office market

The City of London is a major financial centre where the property market is heavily dependent on the space requirements of office occupiers. Technological change, however, is changing the way in which organisations conduct their business and is challenging the continued locational pull of the City. This research presents findings from a major survey of City occupiers carried out by The College research team during 2002. The research examines how the shape and form of the office property market in the City will be affected by process change in eBusiness and related technology over the next 5 years. The report, which includes an extensive literature review, examines the implications of increased homeworking and other trends for future office supply in the City. The research was funded by the Worshipful Company of Chartered Surveyors Trust (Toby Sutton Research Award), and part of the literature review by the Small Business Support Research Unit of DTI. It is essential reading for surveyors, planners, facilities managers and all those interested in the technology and property interface.

On the application of optimal wavelet filter banks for ECG signal classification

This paper discusses ECG signal classification after parametrizing the ECG waveforms in the wavelet domain. Signal decomposition using perfect reconstruction quadrature mirror filter banks can provide a very parsimonious representation of ECG signals. In the current work, the filter parameters are adjusted by a numerical optimization algorithm in order to minimize a cost function associated to the filter cut-off sharpness. The goal consists of achieving a better compromise between frequency selectivity and time resolution at each decomposition level than standard orthogonal filter banks such as those of the Daubechies and Coiflet families. Our aim is to optimally decompose the signals in the wavelet domain so that they can be subsequently used as inputs for training to a neural network classifier.

Stereochemistry and thermal stability of tartaric acid on the intrinsically chiral Cu{531} surface

Intrinsically chiral metal surfaces provide enantiospecific reaction environments without the need of coadsorbed modifiers. Amongst the intrinsically chiral copper surfaces, Cu{531} has the smallest unit cell and the highest density of chiral sites. XPS, NEXAFS and TPD were employed to investigate the adsorption and decomposition behaviour of the two chiral enantiomers of tartaric acid on this surface. The results obtained from XPS and NEXAFS show that at saturation coverage both enantiomers of tartaric acid adsorb in a μ4 configuration through the two carboxylic groups,which are rotatedwith respect to each other by 90°±≈15°within the surface plane. At intermediate coverage the R,R enantiomer adopts a similar configuration, but the S,S enantiomer is different and shows a high degree of dissociation. Growth of multilayers is observed at high exposures when the sample is kept at below 370 K. TPD experiments show that multilayers desorb between 390 K and 470 K and decomposition of the chemisorbed layer occurs between 470 K and 600 K. The desorption spectra support a two-step decomposition mechanism with a O_C_C_O or HO–HC_CH–OH intermediate that leads to production of CO2 and CO. Enantiomeric differences are observed in the desorption features related to the decomposition of the chemisorbed layer.

Mesh adaptation on the sphere using optimal transport and the numerical solution of a Monge-Ampère type equation

An equation of Monge-Ampère type has, for the first time, been solved numerically on the surface of the sphere in order to generate optimally transported (OT) meshes, equidistributed with respect to a monitor function. Optimal transport generates meshes that keep the same connectivity as the original mesh, making them suitable for r-adaptive simulations, in which the equations of motion can be solved in a moving frame of reference in order to avoid mapping the solution between old and new meshes and to avoid load balancing problems on parallel computers. The semi-implicit solution of the Monge-Ampère type equation involves a new linearisation of the Hessian term, and exponential maps are used to map from old to new meshes on the sphere. The determinant of the Hessian is evaluated as the change in volume between old and new mesh cells, rather than using numerical approximations to the gradients. OT meshes are generated to compare with centroidal Voronoi tesselations on the sphere and are found to have advantages and disadvantages; OT equidistribution is more accurate, the number of iterations to convergence is independent of the mesh size, face skewness is reduced and the connectivity does not change. However anisotropy is higher and the OT meshes are non-orthogonal. It is shown that optimal transport on the sphere leads to meshes that do not tangle. However, tangling can be introduced by numerical errors in calculating the gradient of the mesh potential. Methods for alleviating this problem are explored. Finally, OT meshes are generated using observed precipitation as a monitor function, in order to demonstrate the potential power of the technique.

On the importance of Vaisala RS92 radiosonde humidity corrections for a better agreement between measured and modeled satellite radiances

A study has been carried out to assess the importance of radiosonde corrections in improving the agreement between satellite and radiosonde measurements of upper-tropospheric humidity. Infrared [High Resolution Infrared Radiation Sounder (HIRS)-12] and microwave [Advanced Microwave Sounding Unit (AMSU)-18] measurements from the NOAA-17 satellite were used for this purpose. The agreement was assessed by comparing the satellite measurements against simulated measurements using collocated radiosonde profiles of the Atmospheric Radiation Measurement (ARM) Program undertaken at tropical and midlatitude sites. The Atmospheric Radiative Transfer Simulator (ARTS) was used to simulate the satellite radiances. The comparisons have been done under clear-sky conditions, separately for daytime and nighttime soundings. Only Vaisala RS92 radiosonde sensors were used and an empirical correction (EC) was applied to the radiosonde measurements. The EC includes correction for mean calibration bias and for solar radiation error, and it removes radiosonde bias relative to three instruments of known accuracy. For the nighttime dataset, the EC significantly reduces the bias from 0.63 to 20.10 K in AMSU-18 and from 1.26 to 0.35 K in HIRS-12. The EC has an even greater impact on the daytime dataset with a bias reduction from 2.38 to 0.28 K in AMSU-18 and from 2.51 to 0.59 K in HIRS-12. The present study promises a more accurate approach in future radiosonde-based studies in the upper troposphere.

The effects of corporate and country sustainability characteristics on the cost of debt: an international investigation

We investigate the relationship between corporate and country sustainability on the cost of bank loans. We look into 470 loan agreements signed between 2005 and 2012 with borrowers based in 28 different countries across the world and operating in all major industries. Our principal findings reveal that country sustainability, relating to both social and environmental frameworks, has a statistically and economically impactful effect on direct financing of economic activity. An increase of one unit in a country's sustainability score is associated with an average decrease in the cost of debt by 64 basis points. Our international analysis shows that the environmental dimension of a country's institutional framework is approximately twice as impactful as the social dimension, when it comes to determining the cost of corporate loans. On the other hand, we find no conclusive evidence that firm-level sustainability influences the interest rates charged to borrowing firms by banks. Our main findings survive a battery of robustness tests and additional analyses concerning subsamples, alternative sustainability metrics and the effects of financial crisis.