Synthesis, x-ray structure and anion binding properties of a cryptand-like hybrid calixpyrrole

The novel cryptand in/out-3, containing two tripyrrolemethane units briged by three 1,3- diisopropylidenbenzene arms was readily synthesized by a convergent three-step synthesis. It binds fluoride by inclusion with excellent selectivity with respect to a number of other tested anions. The structure of the free receptor and that of its fluoride complex were investigated in solution by NMR spectroscopy. The solid state X-ray structure of the free cryptand 3 was also determined.

Redox-active polymers based on nonbridged metal−metal bonds. Electrochemical formation of [Os(bpy)(CO)(L)]n(bpy = 2,2‘-bipyridine; L = CO, MeCN) and of their reduced forms: a spectroelectrochemical study

IR, UV-vis, and EPR spectroelectrochemistry at variable temperatures and in different solvents were applied to investigate in situ the formation of electroactive molecular chains with a nonbridged Os-Os backbone, in particular, the polymer [Os-0(bpy)(CO)(2)](n), (bpy = 2,2'-bipyridine), from a mononuclear Os(II) carbonyl precursor, [Os-II(bpy)(CO)(2)Cl-2]. The one-electron-reduced form, [Os-II(bpy(.-))(CO)(2)Cl-2](-), has been characterized spectroscopically at low temperatures. This radical anion is the key intermediate in the electrochemical propagation process responsible for the metal-metal bond formation. Unambiguous spectroscopic evidence has been gained also for the formation of [{Os-0(bpy(.-))(CO)(2)}(-)](n), the electron-rich electrocatalyst of CO2 reduction. The polymer species are fairly well soluble in butyronitrile, which is important for their potential utilization in nanoscience, for example, as conducting molecular wires. We have also shown that complete solubility is accomplished for the monocarbonyl-acetonitrile derivative of the polymer, [Os-0(bpy)(CO)(MeCN)(2)Cl](n).

Self-organising neural networks for adaptive control

Self-organizing neural networks have been implemented in a wide range of application areas such as speech processing, image processing, optimization and robotics. Recent variations to the basic model proposed by the authors enable it to order state space using a subset of the input vector and to apply a local adaptation procedure that does not rely on a predefined test duration limit. Both these variations have been incorporated into a new feature map architecture that forms an integral part of an Hybrid Learning System (HLS) based on a genetic-based classifier system. Problems are represented within HLS as objects characterized by environmental features. Objects controlled by the system have preset targets set against a subset of their features. The system's objective is to achieve these targets by evolving a behavioural repertoire that efficiently explores and exploits the problem environment. Feature maps encode two types of knowledge within HLS — long-term memory traces of useful regularities within the environment and the classifier performance data calibrated against an object's feature states and targets. Self-organization of these networks constitutes non-genetic-based (experience-driven) learning within HLS. This paper presents a description of the HLS architecture and an analysis of the modified feature map implementing associative memory. Initial results are presented that demonstrate the behaviour of the system on a simple control task.

A hybrid data assimilation scheme for model parameter estimation: application to morphodynamic modelling

We present a novel algorithm for joint state-parameter estimation using sequential three dimensional variational data assimilation (3D Var) and demonstrate its application in the context of morphodynamic modelling using an idealised two parameter 1D sediment transport model. The new scheme combines a static representation of the state background error covariances with a flow dependent approximation of the state-parameter cross-covariances. For the case presented here, this involves calculating a local finite difference approximation of the gradient of the model with respect to the parameters. The new method is easy to implement and computationally inexpensive to run. Experimental results are positive with the scheme able to recover the model parameters to a high level of accuracy. We expect that there is potential for successful application of this new methodology to larger, more realistic models with more complex parameterisations.

A robust hybrid feedback active noise cancellation headset

This paper investigates the robustness of a hybrid analog/digital feedback active noise cancellation (ANC) headset system. The digital ANC systems with the filtered-x least-mean-square (FXLMS) algorithm require accurate estimation of the secondary path for the stability and convergence of the algorithm. This demands a great challenge for the ANC headset design because the secondary path may fluctuate dramatically such as when the user adjusts the position of the ear-cup. In this paper, we analytically show that adding an analog feedback loop into the digital ANC systems can effectively reduce the plant fluctuation, thus achieving a more robust system. The method for designing the analog controller is highlighted. A practical hybrid analog/digital feedback ANC headset has been built and used to conduct experiments, and the experimental results show that the hybrid headset system is more robust under large plant fluctuation, and has achieved satisfactory noise cancellation for both narrowband and broadband noises.

Bronze Age barrows on the heathlands of southern England: construction, forms and interpretations

The Bronze Age barrows on the downs of southern England have been investigated and discussed for nearly 200 years, but much less attention has been paid to similar structures in the areas of heathland beyond the chalk and river gravels. They were built in a phase of expansion towards the end of the Early Bronze Age, and more were constructed during the Middle Bronze Age. They have a number of distinctive characteristics. This paper considers the interpretation of these monuments and their wider significance in relation to the pattern of settlement. It also discusses the origins of field systems in lowland England.

Implementation of robust hybrid feedback FxLMS active noise cancellation headset

Instability is a serious problem for acoustic Active Noise Cancellation (ANC) headsets as a result of large errors in estimating the transfer function of the plant. Typically this occurs when, for example, a wearer adjusts the headset. In this paper, the instability problem of adaptive ANC headset is addressed. To ensure stability of the whole system, we propose a hybrid solution consisting of an analog feedback loop parallel to the digital loop, and the role of the analog loop in stabilizing the headset is analyzed theoretically. Finally the methodology of implementing such a hybrid ANC headset is described in detail. The experiments carried out on the headset prototype show that the headset is robust under considerable fluctuations of the plant transfer characteristics, and has very good noise cancellation performance both for narrow-band and wide-band disturbances.

Puroindoline-a, a lipid binding protein from common wheat, spontaneously forms prolate protein micelles in solution

The self-assembly in solution of puroindoline-a (Pin-a), an amphiphilic lipid binding protein from common wheat, was investigated by small angle neutron scattering, dynamic light scattering and size exclusion chromatography. Pin-a was found to form monodisperse prolate ellipsoidal micelles with a major axial radius of 112 +/- 4.5 A ˚ and minor axial radius of 40.4 +/- 0.18 A ˚ . These protein micelles were formed by the spontaneous self-assembly of 38 Pin-a molecules in solution and were stable over a wide pH range (3.5–11) and at elevated temperatures (20–65 degC). Pin-a micelles could be disrupted upon addition of the non-ionic surfactant dodecyl-b-maltoside, suggesting that the protein self-assembly is driven by hydrophobic forces, consisting of intermolecular interactions between Trp residues located within a well-defined Trp-rich domain of Pin-a.

Plastic compression of a collagen gel forms a much improved scaffold for ocular surface tissue engineering over conventional collagen gels

We compare the use of plastically compressed collagen gels to conventional collagen gels as scaffolds onto which corneal limbal epithelial cells (LECs) are seeded to construct an artificial corneal epithelium. LECs were isolated from bovine corneas (limbus) and seeded onto either conventional uncompressed or novel compressed collagen gels and grown in culture. Scanning electron microscopy (SEM) results showed that fibers within the uncompressed gel were loose and irregularly ordered, whereas the fibers within the compressed gel were densely packed and more evenly arranged. Quantitative analysis of LECs expansion across the surface of the two gels showed similar growth rates (p > 0.05). Under SEM, the LECs, expanded on uncompressed gels, showed a rough and heterogeneous morphology, whereas on the compressed gel, the cells displayed a smooth and homogeneous morphology. Transmission electron microscopy (TEM) results showed the compressed scaffold to contain collagen fibers of regular diameter and similar orientation resembling collagen fibers within the normal cornea. TEM and light microscopy also showed that cell–cell and cell–matrix attachment, stratification, and cell density were superior in LECs expanded upon compressed collagen gels. This study demonstrated that the compressed collagen gel was an excellent biomaterial scaffold highly suited to the construction of an artificial corneal epithelium and a significant improvement upon conventional collagen gels.