A unique example of structural and magnetic diversity in four interconvertible copper(II)−azide complexes with the same Schiff base ligand: a monomer, a dimer, a chain, and a layer

Four new Cu(II)-azido complexes of formula [CuL(N-3)] (1), [CuL(N-3)](2) (2), [Cu7L2(N-3)(12)](n) (3), and [Cu2L(dmen)-(N-3)(3)](n) (4) (dmen = N,N-dimethylethylenediamine) have been synthesized using the same tridentate Schiff base ligand HL (2-[1-(2-dimethylaminoethylimino)ethyl]phenol, the condensation product of dmen and 2-hydroxyacetophenone). The four compounds have been characterized by X-ray structural analyses and variable-temperature magnetic susceptibility measurements. Complex 1 is mononuclear, whereas 2 is a single mu-1,1 azido-bridged dinuclear compound. The polymeric compound 3 possesses a 2D structure in which the Cu(II) ions are linked by phenoxo oxygen atoms and two different azide bridges (mu-1,1 and mu-1,1,3). The structure of complex 4 is a double helix in which two mu-1,3-azido-bridged alternating one-dimensional helical chains of CuL(N-3) and Cu(dmen)(N-3)(2) are joined together by weak mu-1,1 azido bridges and H-bonds. The complexes interconvert in solution and can be obtained in pure form by carefully controlling the conditions. The magnetic properties of compounds 1 and 2 show the presence of very weak antiferromagnetic exchange interactions mediated by a ligand pi overlap (J = -1.77) and by an asymmetric 1,1-N-3 bridge (J = -1.97 cm(-1)), respectively. Compound 3 presents, from the magnetic point of view, a decorated chain structure with both ferro- and antiferromagnetic interactions. Compound 4 is an alternating helicoidal chain with two weak antiferromagnetic exchange interactions (J -1.35 and -2.64 cm(-1)).

Optimising memory usage in n-tuple neural networks

The use of n-tuple or weightless neural networks as pattern recognition devices is well known (Aleksander and Stonham, 1979). They have some significant advantages over the more common and biologically plausible networks, such as multi-layer perceptrons; for example, n-tuple networks have been used for a variety of tasks, the most popular being real-time pattern recognition, and they can be implemented easily in hardware as they use standard random access memories. In operation, a series of images of an object are shown to the network, each being processed suitably and effectively stored in a memory called a discriminator. Then, when another image is shown to the system, it is processed in a similar manner and the system reports whether it recognises the image; is the image sufficiently similar to one already taught? If the system is to be able to recognise and discriminate between m-objects, then it must contain m-discriminators. This can require a great deal of memory. This paper describes various ways in which memory requirements can be reduced, including a novel method for multiple discriminator n-tuple networks used for pattern recognition. By using this method, the memory normally required to handle m-objects can be used to recognise and discriminate between 2^m — 2 objects.

Hardware development of the Yorick series of active vision systems

This paper presents a review of the design and development of the Yorick series of active stereo camera platforms and their integration into real-time closed loop active vision systems, whose applications span surveillance, navigation of autonomously guided vehicles (AGVs), and inspection tasks for teleoperation, including immersive visual telepresence. The mechatronic approach adopted for the design of the first system, including head/eye platform, local controller, vision engine, gaze controller and system integration, proved to be very successful. The design team comprised researchers with experience in parallel computing, robot control, mechanical design and machine vision. The success of the project has generated sufficient interest to sanction a number of revisions of the original head design, including the design of a lightweight compact head for use on a robot arm, and the further development of a robot head to look specifically at increasing visual resolution for visual telepresence. The controller and vision processing engines have also been upgraded, to include the control of robot heads on mobile platforms and control of vergence through tracking of an operator's eye movement. This paper details the hardware development of the different active vision/telepresence systems.

A specific pole placement technique to minimise hardware requirements within a real time terrestrial and cable video echo canceller

The real time hardware architecture of a deterministic video echo canceller (deghoster) system is presented. The deghoster is capable of calculating all the multipath channel distortion characteristics from terrestrial and cable television in one single pass while performing real time video in-line ghost cancellation. The results from the actual system are also presented in this paper.

Generation of inertia-gravity waves in the rotating thermal annulus by a localised boundary layer instability

Waves with periods shorter than the inertial period exist in the atmosphere (as inertia-gravity waves) and in the oceans (as Poincaré and internal gravity waves). Such waves owe their origin to various mechanisms, but of particular interest are those arising either from local secondary instabilities or spontaneous emission due to loss of balance. These phenomena have been studied in the laboratory, both in the mechanically-forced and the thermally-forced rotating annulus. Their generation mechanisms, especially in the latter system, have not yet been fully understood, however. Here we examine short period waves in a numerical model of the rotating thermal annulus, and show how the results are consistent with those from earlier laboratory experiments. We then show how these waves are consistent with being inertia-gravity waves generated by a localised instability within the thermal boundary layer, the location of which is determined by regions of strong shear and downwelling at certain points within a large-scale baroclinic wave flow. The resulting instability launches small-scale inertia-gravity waves into the geostrophic interior of the flow. Their behaviour is captured in fully nonlinear numerical simulations in a finite-difference, 3D Boussinesq Navier-Stokes model. Such a mechanism has many similarities with those responsible for launching small- and meso-scale inertia-gravity waves in the atmosphere from fronts and local convection.

Coupling thin layer electrochemistry with epifluorescence microscopy: an expedient way of investigating electrofluorochromism of organic dyes

The first example of thin layer electrochemistry coupled to epifluorescence microscopy in the total internal reflectance mode is described and applied to the investigation of electrochemically modulated fluorescence of an organic dye (chloromethoxytetrazine) in solution. This technique allows to generate full redox switch of fluorescence when converting reversibly the dye into its anion radical, as well as to record the spectral features of the electrogenerated species. Recording simultaneously fluorescence intensity and lifetime along with coulombic charge as a function of the electrode potential will lead to a deep insight into the redox quenching mechanism.

Boundary layer dynamics over London, UK, as observed using Doppler lidar during REPARTEE-II

Urban boundary layers (UBLs) can be highly complex due to the heterogeneous roughness and heating of the surface, particularly at night. Due to a general lack of observations, it is not clear whether canonical models of boundary layer mixing are appropriate in modelling air quality in urban areas. This paper reports Doppler lidar observations of turbulence profiles in the centre of London, UK, as part of the second REPARTEE campaign in autumn 2007. Lidar-measured standard deviation of vertical velocity averaged over 30 min intervals generally compared well with in situ sonic anemometer measurements at 190 m on the BT telecommunications Tower. During calm, nocturnal periods, the lidar underestimated turbulent mixing due mainly to limited sampling rate. Mixing height derived from the turbulence, and aerosol layer height from the backscatter profiles, showed similar diurnal cycles ranging from c. 300 to 800 m, increasing to c. 200 to 850 m under clear skies. The aerosol layer height was sometimes significantly different to the mixing height, particularly at night under clear skies. For convective and neutral cases, the scaled turbulence profiles resembled canonical results; this was less clear for the stable case. Lidar observations clearly showed enhanced mixing beneath stratocumulus clouds reaching down on occasion to approximately half daytime boundary layer depth. On one occasion the nocturnal turbulent structure was consistent with a nocturnal jet, suggesting a stable layer. Given the general agreement between observations and canonical turbulence profiles, mixing timescales were calculated for passive scalars released at street level to reach the BT Tower using existing models of turbulent mixing. It was estimated to take c. 10 min to diffuse up to 190 m, rising to between 20 and 50 min at night, depending on stability. Determination of mixing timescales is important when comparing to physico-chemical processes acting on pollutant species measured simultaneously at both the ground and at the BT Tower during the campaign. From the 3 week autumnal data-set there is evidence for occasional stable layers in central London, effectively decoupling surface emissions from air aloft.

Kinetics of layer hopping in a diblock copolymer lamellar phase

In the ordered state, symmetric diblock copolymers self-assemble into an anisotropic lamellar morphology. The equilibrium thickness of the lamellae is the result of a delicate balance between enthalpic and entropic energies, which can be tuned by controlling the temperature. Here we devise a simple yet powerful method of detecting tiny changes in the lamellar thickness using optical microscopy. From such measurements we characterize the enthalpic interaction as well as the kinetics of molecules as they hop from one layer to the next in order to adjust the lamellar thickness in response to a temperature jump. The resolution of the measurements facilitate a direct comparison to predictions from self-consistent field theory.

Multi-layer radial basis function networks: an extension to the radial basis function

This paper presents the initial research carried out into a new neural network called the multilayer radial basis function network (MRBF). The network extends the radial basis function (RBF) in a similar way to that in which the multilayer perceptron extends the perceptron. It is hoped that by connecting RBFs together in a layered fashion, an equivalent increase in ability can be gained, as is gained from using MLPs instead of single perceptrons. The results of a practical comparison between individual RBFs and MRBF's are also given.

Multiband OFDM modulation and demodulation for ultra wideband communications

This chapter considers the Multiband Orthogonal Frequency Division Multiplexing (MB- OFDM) modulation and demodulation with the intention to optimize the Ultra-Wideband (UWB) system performance. OFDM is a type of multicarrier modulation and becomes the most important aspect for the MB-OFDM system performance. It is also a low cost digital signal component efficiently using Fast Fourier Transform (FFT) algorithm to implement the multicarrier orthogonality. Within the MB-OFDM approach, the OFDM modulation is employed in each 528 MHz wide band to transmit the data across the different bands while also using the frequency hopping technique across different bands. Each parallel bit stream can be mapped onto one of the OFDM subcarriers. Quadrature Phase Shift Keying (QPSK) and Dual Carrier Modulation (DCM) are currently used as the modulation schemes for MB-OFDM in the ECMA-368 defined UWB radio platform. A dual QPSK soft-demapper is suitable for ECMA-368 that exploits the inherent Time-Domain Spreading (TDS) and guard symbol subcarrier diversity to improve the receiver performance, yet merges decoding operations together to minimize hardware and power requirements. There are several methods to demap the DCM, which are soft bit demapping, Maximum Likelihood (ML) soft bit demapping, and Log Likelihood Ratio (LLR) demapping. The Channel State Information (CSI) aided scheme coupled with the band hopping information is used as a further technique to improve the DCM demapping performance. ECMA-368 offers up to 480 Mb/s instantaneous bit rate to the Medium Access Control (MAC) layer, but depending on radio channel conditions dropped packets unfortunately result in a lower throughput. An alternative high data rate modulation scheme termed Dual Circular 32-QAM that fits within the configuration of the current standard increasing system throughput thus maintaining the high rate throughput even with a moderate level of dropped packets.

Advances in continuously profiling the thermodynamic state of the boundary layer: integration of measurements and methods

This paper describes advances in ground-based thermodynamic profiling of the lower troposphere through sensor synergy. The well-documented integrated profiling technique (IPT), which uses a microwave profiler, a cloud radar, and a ceilometer to simultaneously retrieve vertical profiles of temperature, humidity, and liquid water content (LWC) of nonprecipitating clouds, is further developed toward an enhanced performance in the boundary layer and lower troposphere. For a more accurate temperature profile, this is accomplished by including an elevation scanning measurement modus of the microwave profiler. Height-dependent RMS accuracies of temperature (humidity) ranging from 0.3 to 0.9 K (0.5–0.8 g m−3) in the boundary layer are derived from retrieval simulations and confirmed experimentally with measurements at distinct heights taken during the 2005 International Lindenberg Campaign for Assessment of Humidity and Cloud Profiling Systems and its Impact on High-Resolution Modeling (LAUNCH) of the German Weather Service. Temperature inversions, especially of the lower boundary layer, are captured in a very satisfactory way by using the elevation scanning mode. To improve the quality of liquid water content measurements in clouds the authors incorporate a sophisticated target classification scheme developed within the European cloud observing network CloudNet. It allows the detailed discrimination between different types of backscatterers detected by cloud radar and ceilometer. Finally, to allow IPT application also to drizzling cases, an LWC profiling method is integrated. This technique classifies the detected hydrometeors into three different size classes using certain thresholds determined by radar reflectivity and/or ceilometer extinction profiles. By inclusion into IPT, the retrieved profiles are made consistent with the measurements of the microwave profiler and an LWC a priori profile. Results of IPT application to 13 days of the LAUNCH campaign are analyzed, and the importance of integrated profiling for model evaluation is underlined.

Kinetic multi-layer model of gas-particle interactions in aerosols and clouds (KM-GAP): linking condensation, evaporation and chemical reactions of organics, oxidants and water

We present a novel kinetic multi-layer model for gas-particle interactions in aerosols and clouds (KM-GAP) that treats explicitly all steps of mass transport and chemical reaction of semi-volatile species partitioning between gas phase, particle surface and particle bulk. KM-GAP is based on the PRA model framework (Pöschl-Rudich-Ammann, 2007), and it includes gas phase diffusion, reversible adsorption, surface reactions, bulk diffusion and reaction, as well as condensation, evaporation and heat transfer. The size change of atmospheric particles and the temporal evolution and spatial profile of the concentration of individual chemical species can be modelled along with gas uptake and accommodation coefficients. Depending on the complexity of the investigated system, unlimited numbers of semi-volatile species, chemical reactions, and physical processes can be treated, and the model shall help to bridge gaps in the understanding and quantification of multiphase chemistry and microphysics in atmo- spheric aerosols and clouds. In this study we demonstrate how KM-GAP can be used to analyze, interpret and design experimental investigations of changes in particle size and chemical composition in response to condensation, evaporation, and chemical reaction. For the condensational growth of water droplets, our kinetic model results provide a direct link between laboratory observations and molecular dynamic simulations, confirming that the accommodation coefficient of water at 270 K is close to unity. Literature data on the evaporation of dioctyl phthalate as a function of particle size and time can be reproduced, and the model results suggest that changes in the experimental conditions like aerosol particle concentration and chamber geometry may influence the evaporation kinetics and can be optimized for eðcient probing of specific physical effects and parameters. With regard to oxidative aging of organic aerosol particles, we illustrate how the formation and evaporation of volatile reaction products like nonanal can cause a decrease in the size of oleic acid particles exposed to ozone.

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.