Spectroscopic properties and electronic structures of 17-electron half-sandwich ruthenium acetylide complexes, [Ru(CCAr)(L2)Cp′]+ (Ar=phenyl, p-tolyl, 1-naphthyl, 9-anthryl; L2=(PPh3)2, Cp′=Cp; L2=dppe; Cp′=Cp∗)

A series of half-sandwich bis(phosphine) ruthenium acetylide complexes [Ru(C CAr)(L-2)Cp'] (Ar = phenyl, p-tolyl, 1-naphthyl, 9-anthryl; L2 = (PPh3)(2), Cp' = Cp; L-2 = dppe; Cp' = Cp*) have been examined using electrochemical and spectroelectrochemical methods. One-electron oxidation of these complexes gave the corresponding radical cations [Ru(C CAr)(L2)Cp'](+). Those cations based on Ru(dppe)Cp*, or which feature a para-tolyl acetylide substituent, are more chemically robust than examples featuring the Ru(PPh3)(2)Cp moiety, permitting good quality UV-Vis-NIR and IR spectroscopic data to be obtained using spectroelectrochemical methods. On the basis of TD DFT calculations, the low energy (NIR) absorption bands in the experimental electronic spectra for most of these radical cations are assigned to transitions between the beta-HOSO and beta-LUSO, both of which have appreciable metal d and ethynyl pi character. However, the large contribution from the anthryl moiety to the frontier orbitals of [Ru(C CC14H9)(L2)CP'](+) suggests compounds containing this moiety should be described as metal-stabilised anthryl radical cations.

Neural network feature maps for Chinese phonemes

It has been shown through a number of experiments that neural networks can be used for a phonetic typewriter. Algorithms can be looked on as producing self-organizing feature maps which correspond to phonemes. In the Chinese language the utterance of a Chinese character consists of a very simple string of Chinese phonemes. With this as a starting point, a neural network feature map for Chinese phonemes can be built up. In this paper, feature map structures for Chinese phonemes are discussed and tested. This research on a Chinese phonetic feature map is important both for Chinese speech recognition and for building a Chinese phonetic typewriter.

Metal cluster expansion by addition of low valent group 14 reagents: III. Reaction of bis[bis(trimethylsilyl)methyl]tin with M3(CO)12 or its derivatives (M = Fe, Ru, or Os): the crystal and molecular structures of M3(μ-SnR2)2(CO)10(R = CH(SiMe3)2; M = Ru or Os)

The stannylene [SnR2] (R = CH(SiMe3)2) reacts in different ways with the three dodecacarbonyls of the iron triad: [Fe3(CO)12] gives [Fe2(CO)8(μ-SnR2)], [Ru3(CO)12] gives the planar pentametallic cluster [Ru3(CO)10(μ-SnR2)2], for which a full structural analysis is reported, while [Os3(CO)12] fails to react. Different products are also obtained from three nitrile derivatives: [Fe3-(CO)11(MeCN)] gives [Fe2(CO)6(μ-SnR2)2], which has a structure significantly different from that of known Fe2Sn2 clusters, [Ru3(CO)10(MeCN)2] gives the pentametallic cluster described above, while [Os3(CO)10(MeCN)2] gives the isostructural osmium analogue, which shows the unusual feature of a CO group bridging two osmium atoms.

A two-dimensional X-ray scattering system for in-situ time-resolving studies of polymer structures subjected to controlled deformations

A two-dimensional X-ray scattering system developed around a CCD-based area detector is presented, both in terms of hardware employed and software designed and developed. An essential feature is the integration of hardware and software, detection and sample environment control which enables time-resolving in-situ wide-angle X-ray scattering measurements of global structural and orientational parameters of polymeric systems subjected to a variety of controlled external fields. The development and operation of a number of rheometers purpose-built for the application of such fields are described. Examples of the use of this system in monitoring degrees of shear-induced orientation in liquid-crystalline systems and crystallization of linear polymers subsequent to shear flow are presented.

Hollow structures with bilayer graphene walls

The formation of three-dimensional shell-like structures with bilayer graphene walls is described. The structures are produced by the passage of an electric current through graphite in an arc-discharge apparatus. High resolution transmission electron microscopy is used to characterize the carbon, and provides evidence that the structures are three-dimensional rather than flat. A striking feature of the material is that it contains bilayer nanotubes seamlessly joined to larger shell-like regions. The possible growth mechanism of the carbon is discussed, and potential applications considered.

Molecular archaeology of Flaviviridae untranslated regions: duplicated RNA structures in the replication enhancer of flaviviruses and pestiviruses emerged via convergent evolution.

RNA secondary structures in the 3'untranslated regions (3'UTR) of the viruses of the family Flaviviridae, previously identified as essential (promoters) or beneficial (enhancers) for replication, have been analysed. Duplicated enhancer elements are revealed as a global feature in the evolution of the 3'UTR of distantly related viruses within the genera Flavivirus and Pestivirus. For the flaviviruses, duplicated structures occur in the 3'UTR of all four distantly related ecological virus subgroups (tick-borne, mosquito-borne, no known vector and insect-specific flaviviruses (ISFV). RNA structural differences distinguish tick-borne flaviviruses with discrete pathogenetic characteristics. For Aedes- and Culex-associated ISFV, secondary RNA structures with different conformations display numerous short ssRNA direct repeats, exposed as loops and bulges. Long quadruplicate regions comprise almost the entire 3'UTR of Culex-associated ISFV. Extended duplicated sequence and associated RNA structures were also discovered in the 3'UTR of pestiviruses. In both the Flavivirus and Pestivirus genera, duplicated RNA structures were localized to the enhancer regions of the 3'UTR suggesting an adaptive role predominantly in wild-type viruses. We propose sequence reiteration might act as a scaffold for dimerization of proteins involved in assembly of viral replicase complexes. Numerous nucleotide repeats exposed as loops/bulges might also interfere with host immune responses acting as a molecular sponge to sequester key host proteins or microRNAs.

Sensitivity of feature-based analysis methods of storm tracks to the form of background field removal

For the tracking of extrema associated with weather systems to be applied to a broad range of fields it is necessary to remove a background field that represents the slowly varying, large spatial scales. The sensitivity of the tracking analysis to the form of background field removed is explored for the Northern Hemisphere winter storm tracks for three contrasting fields from an integration of the U. K. Met Office's (UKMO) Hadley Centre Climate Model (HadAM3). Several methods are explored for the removal of a background field from the simple subtraction of the climatology, to the more sophisticated removal of the planetary scales. Two temporal filters are also considered in the form of a 2-6-day Lanczos filter and a 20-day high-pass Fourier filter. The analysis indicates that the simple subtraction of the climatology tends to change the nature of the systems to the extent that there is a redistribution of the systems relative to the climatological background resulting in very similar statistical distributions for both positive and negative anomalies. The optimal planetary wave filter removes total wavenumbers less than or equal to a number in the range 5-7, resulting in distributions more easily related to particular types of weather system. For the temporal filters the 2-6-day bandpass filter is found to have a detrimental impact on the individual weather systems, resulting in the storm tracks having a weak waveguide type of behavior. The 20-day high-pass temporal filter is less aggressive than the 2-6-day filter and produces results falling between those of the climatological and 2-6-day filters.

Adaptive constraints for feature tracking

In this paper extensions to an existing tracking algorithm are described. These extensions implement adaptive tracking constraints in the form of regional upper-bound displacements and an adaptive track smoothness constraint. Together, these constraints make the tracking algorithm more flexible than the original algorithm (which used fixed tracking parameters) and provide greater confidence in the tracking results. The result of applying the new algorithm to high-resolution ECMWF reanalysis data is shown as an example of its effectiveness.

Feature-point detection using distance transforms: Application to tracking tropical convective complexes

The identification, tracking, and statistical analysis of tropical convective complexes using satellite imagery is explored in the context of identifying feature points suitable for tracking. The feature points are determined based on the shape of complexes using the distance transform technique. This approach has been applied to the determination feature points for tropical convective complexes identified in a time series of global cloud imagery. The feature points are used to track the complexes, and from the tracks statistical diagnostic fields are computed. This approach allows the nature and distribution of organized deep convection in the Tropics to be explored.

Feature tracking on the unit-sphere

Techniques used in a previous study of the objective identification and tracking of meteorological features in model data are extended to the unit sphere. An alternative feature detection scheme is described based on cubic interpolation for the sphere and local maximization. The extension of the tracking technique, used in the previous study, to the unit sphere is described. An example of the application of these techniques to a global relative vorticity field from a model integration are presented and discussed.

A comparison of recent reanalysis datasets using objective feature tracking: Storm tracks and tropical easterly waves

Data from four recent reanalysis projects [ECMWF, NCEP-NCAR, NCEP - Department of Energy ( DOE), NASA] have been diagnosed at the scale of synoptic weather systems using an objective feature tracking method. The tracking statistics indicate that, overall, the reanalyses correspond very well in the Northern Hemisphere (NH) lower troposphere, although differences for the spatial distribution of mean intensities show that the ECMWF reanalysis is systematically stronger in the main storm track regions but weaker around major orographic features. A direct comparison of the track ensembles indicates a number of systems with a broad range of intensities that compare well among the reanalyses. In addition, a number of small-scale weak systems are found that have no correspondence among the reanalyses or that only correspond upon relaxing the matching criteria, indicating possible differences in location and/or temporal coherence. These are distributed throughout the storm tracks, particularly in the regions known for small-scale activity, such as secondary development regions and the Mediterranean. For the Southern Hemisphere (SH), agreement is found to be generally less consistent in the lower troposphere with significant differences in both track density and mean intensity. The systems that correspond between the various reanalyses are considerably reduced and those that do not match span a broad range of storm intensities. Relaxing the matching criteria indicates that there is a larger degree of uncertainty in both the location of systems and their intensities compared with the NH. At upper-tropospheric levels, significant differences in the level of activity occur between the ECMWF reanalysis and the other reanalyses in both the NH and SH winters. This occurs due to a lack of coherence in the apparent propagation of the systems in ERA15 and appears most acute above 500 hPa. This is probably due to the use of optimal interpolation data assimilation in ERA15. Also shown are results based on using the same techniques to diagnose the tropical easterly wave activity. Results indicate that the wave activity is sensitive not only to the resolution and assimilation methods used but also to the model formulation.

Convectively coupled equatorial waves: A new methodology for identifying wave structures in observational data

Convectively coupled equatorial waves are fundamental components of the interaction between the physics and dynamics of the tropical atmosphere. A new methodology, which isolates individual equatorial wave modes, has been developed and applied to observational data. The methodology assumes that the horizontal structures given by equatorial wave theory can be used to project upper- and lower-tropospheric data onto equatorial wave modes. The dynamical fields are first separated into eastward- and westward-moving components with a specified domain of frequency–zonal wavenumber. Each of the components for each field is then projected onto the different equatorial modes using the y structures of these modes given by the theory. The latitudinal scale yo of the modes is predetermined by data to fit the equatorial trapping in a suitable latitude belt y = ±Y. The extent to which the different dynamical fields are consistent with one another in their depiction of each equatorial wave structure determines the confidence in the reality of that structure. Comparison of the analyzed modes with the eastward- and westward-moving components in the convection field enables the identification of the dynamical structure and nature of convectively coupled equatorial waves. In a case study, the methodology is applied to two independent data sources, ECMWF Reanalysis and satellite-observed window brightness temperature (Tb) data for the summer of 1992. Various convectively coupled equatorial Kelvin, mixed Rossby–gravity, and Rossby waves have been detected. The results indicate a robust consistency between the two independent data sources. Different vertical structures for different wave modes and a significant Doppler shifting effect of the background zonal winds on wave structures are found and discussed. It is found that in addition to low-level convergence, anomalous fluxes induced by strong equatorial zonal winds associated with equatorial waves are important for inducing equatorial convection. There is evidence that equatorial convection associated with Rossby waves leads to a change in structure involving a horizontal structure similar to that of a Kelvin wave moving westward with it. The vertical structure may also be radically changed. The analysis method should make a very powerful diagnostic tool for investigating convectively coupled equatorial waves and the interaction of equatorial dynamics and physics in the real atmosphere. The results from application of the analysis method for a reanalysis dataset should provide a benchmark against which model studies can be compared.

Water wave scattering by finite arrays of circular structures

The scattering of small amplitude water waves by a finite array of locally axisymmetric structures is considered. Regions of varying quiescent depth are included and their axisymmetric nature, together with a mild-slope approximation, permits an adaptation of well-known interaction theory which ultimately reduces the problem to a simple numerical calculation. Numerical results are given and effects due to regions of varying depth on wave loading and free-surface elevation are presented.