Design, synthesis and computational modelling of aromatic tweezer-molecules as models for chain-folding polymer blends

Novel 'tweezer-type' complexes that exploit the interactions between pi-electron-rich pyrenyl groups and pi-electron deficient diimide units have been designed and synthesised. The component molecules leading to complex formation were accessed readily from commercially available starting materials through short and efficient syntheses. Analysis of the resulting complexes, using the visible charge-transfer band, revealed association constants that increased sequentially from 130 to 11,000 M-1 as increasing numbers of pi-pi-stacking interactions were introduced into the systems. Computational modelling was used to analyse the structures of these complexes, revealing low-energy chain-folded conformations for both components, which readily allow close, multiple pi-pi-stacking and hydrogen bonding to be achieved. In this paper, we give details of our initial studies of these complexes and outline how their behaviour could provide a basis for designing self-healing polymer blends for use in adaptive coating systems. (C) 2008 Elsevier Ltd. All rights reserved.

2D parallel interpenetration of [M-2(bpp)(4)X-4] [M, Fe(II)/Co(II); bpp, 4,4 '-trimethylenedipyridine; X, SCN-SeCN- and N-3(-)] complexes: pseudohalide-dependent conformation of bpp

Three coordination complexes of Co(II)/Fe(II) with 4,4'-trimethylenedipyridine (bpp) and pseudohalides (SCN-, SeCN- and N-3(-)) have been synthesized. The complexes have been characterized by X-ray single crystal structure determination. They are isomorphous having 2D layers in which two independent wavy nets display parallel interwoven structures. Pseudohalide binds metal centers through N terminal and occupies the trans axial positions of the octahedral metal coordination environment. Pseudohalide remains pendant on both sides of the polymeric layer and help the stacking through hydrogen bonding. The conformation of bpp in the interpenetrated nets is observed to be dependent on the choice of pseudohalide. (C) 2008 Elsevier Inc. All rights reserved.

Anion-templated assembly of pseudorotaxanes: importance of anion template, strength of ion-pair thread association, and macrocycle ring size

A wide range of pseuclorotaxane assemblies containing positively charged pyridinium, pyridinium nicotinamide, imidazolium, benzimidazolium and guanidinium threading components, and macrocyclic isophthalamide polyether ligands have been prepared using a general anion templation procedure. In noncompetitive solvent media, coupling halide anion recognition by a macrocyclic ligand with ion-pairing between the halide anion and a strongly associated cation provides the driving force for interpenetration. Extensive solution H-1 NMR binding studies, thermodynamic investigations, and single-crystal X-ray structure determinations reveal that the nature of the halide anion template, strength of the ion-pairing between the anion template and the cationic threading component, and to a lesser extent favorable second sphere pi-pi aromatic stacking interactions between the positively charged threading component and macrocyclic ligand, together with macrocyclic ring size, affect the efficacy of pseudorotaxane formation.

Innovative approach to building systems integration problems: Using systems theory, technological forecasting and scenario planning

Building services are worth about 2% GDP and are essential for the effective and efficient operations of the building. It is increasingly recognised that the value of a building is related to the way it supports the client organisation’s ongoing business operations. Building services are central to the functional performance of buildings and provide the necessary conditions for health, well-being, safety and security of the occupants. They frequently comprise several technologically distinct sub-systems and their design and construction requires the involvement of numerous disciplines and trades. Designers and contractors working on the same project are frequently employed by different companies. Materials and equipment is supplied by a diverse range of manufacturers. Facilities managers are responsible for operation of the building service in use. The coordination between these participants is crucially important to achieve optimum performance, but too often is neglected. This leaves room for serious faults. The need for effective integration is important. Modern technology offers increasing opportunities for integrated personal-control systems for lighting, ventilation and security as well as interoperability between systems. Opportunities for a new mode of systems integration are provided by the emergence of PFI/PPP procurements frameworks. This paper attempts to establish how systems integration can be achieved in the process of designing, constructing and operating building services. The essence of the paper therefore is to envisage the emergent organisational responses to the realisation of building services as an interactive systems network.

A fuzzy multi-criteria decision approach for enhanced auto-tracking of seismic events

The main activity carried out by the geophysicist when interpreting seismic data, in terms of both importance and time spent is tracking (or picking) seismic events. in practice, this activity turns out to be rather challenging, particularly when the targeted event is interrupted by discontinuities such as geological faults or exhibits lateral changes in seismic character. In recent years, several automated schemes, known as auto-trackers, have been developed to assist the interpreter in this tedious and time-consuming task. The automatic tracking tool available in modem interpretation software packages often employs artificial neural networks (ANN's) to identify seismic picks belonging to target events through a pattern recognition process. The ability of ANNs to track horizons across discontinuities largely depends on how reliably data patterns characterise these horizons. While seismic attributes are commonly used to characterise amplitude peaks forming a seismic horizon, some researchers in the field claim that inherent seismic information is lost in the attribute extraction process and advocate instead the use of raw data (amplitude samples). This paper investigates the performance of ANNs using either characterisation methods, and demonstrates how the complementarity of both seismic attributes and raw data can be exploited in conjunction with other geological information in a fuzzy inference system (FIS) to achieve an enhanced auto-tracking performance.

Predicting fault inflow in iterative software development processes: an industrial evaluation

This paper addresses the need for accurate predictions on the fault inflow, i.e. the number of faults found in the consecutive project weeks, in highly iterative processes. In such processes, in contrast to waterfall-like processes, fault repair and development of new features run almost in parallel. Given accurate predictions on fault inflow, managers could dynamically re-allocate resources between these different tasks in a more adequate way. Furthermore, managers could react with process improvements when the expected fault inflow is higher than desired. This study suggests software reliability growth models (SRGMs) for predicting fault inflow. Originally developed for traditional processes, the performance of these models in highly iterative processes is investigated. Additionally, a simple linear model is developed and compared to the SRGMs. The paper provides results from applying these models on fault data from three different industrial projects. One of the key findings of this study is that some SRGMs are applicable for predicting fault inflow in highly iterative processes. Moreover, the results show that the simple linear model represents a valid alternative to the SRGMs, as it provides reasonably accurate predictions and performs better in many cases.

Multiple-model fault tolerant control of terminal unites of HVAC Systems

In this work, a fault-tolerant control scheme is applied to a air handling unit of a heating, ventilation and air-conditioning system. Using the multiple-model approach it is possible to identify faults and to control the system under faulty and normal conditions in an effective way. Using well known techniques to model and control the process, this work focuses on the importance of the cost function in the fault detection and its influence on the reconfigurable controller. Experimental results show how the control of the terminal unit is affected in the presence a fault, and how the recuperation and reconfiguration of the control action is able to deal with the effects of faults.

Pancyclicity of Mobius cubes with faulty nodes

An interconnection network with n nodes is four-pancyclic if it contains a cycle of length l for each integer l with 4 <= l <= n. An interconnection network is fault-tolerant four-pancyclic if the surviving network is four-pancyclic in the presence of faults. The fault-tolerant four-pancyclicity of interconnection networks is a desired property because many classical parallel algorithms can be mapped onto such networks in a communication-efficient fashion, even in the presence of failing nodes or edges. Due to some attractive properties as compared with its hypercube counterpart of the same size, the Mobius cube has been proposed as a promising candidate for interconnection topology. Hsieh and Chen [S.Y. Hsieh, C.H. Chen, Pancyclicity on Mobius cubes with maximal edge faults, Parallel Computing, 30(3) (2004) 407-421.] showed that an n-dimensional Mobius cube is four-pancyclic in the presence of up to n-2 faulty edges. In this paper, we show that an n-dimensional Mobius cube is four-pancyclic in the presence of up to n-2 faulty nodes. The obtained result is optimal in that, if n-1 nodes are removed, the surviving network may not be four-pancyclic. (C) 2005 Elsevier B.V. All rights reserved.

Fast and accurate SCFT calculations for periodic block-copolymer morphologies using the spectral method with Anderson mixing

We study the numerical efficiency of solving the self-consistent field theory (SCFT) for periodic block-copolymer morphologies by combining the spectral method with Anderson mixing. Using AB diblock-copolymer melts as an example, we demonstrate that this approach can be orders of magnitude faster than competing methods, permitting precise calculations with relatively little computational cost. Moreover, our results raise significant doubts that the gyroid (G) phase extends to infinite $\chi N$. With the increased precision, we are also able to resolve subtle free-energy differences, allowing us to investigate the layer stacking in the perforated-lamellar (PL) phase and the lattice arrangement of the close-packed spherical (S$_{cp}$) phase. Furthermore, our study sheds light on the existence of the newly discovered Fddd (O$^{70}$) morphology, showing that conformational asymmetry has a significant effect on its stability.

Self-assembly of a designed amyloid peptide containing the functional thienylalanine unit

The self-assembly of a peptide based on a sequence from the amyloid beta peptide but incorporating the non-natural amino acid beta-2-thienylalanine (2-Thi) has been investigated in aqueous and methanol solutions. The peptide AAKLVFF was used as a design motif, replacing the phenylalanine residues (F) with 2-Thi units to yield (2-Thi)(2-Thi)VLKAA. The 2-Thi residues are expected to confer interesting electronic properties due to charge delocalization and pi-stacking. The peptide is shown to form beta-sheet-rich amyloid fibrils with a twisted morphology, in both water and methanol solutions at sufficiently high concentration. The formation of a self-assembling hydrogel is observed at high concentration. Detailed molecular modeling using molecular dynamics methods was performed using NOE constraints provided by 2D-NMR experiments. The conformational and charge properties of 2-Thi were modeled using quantum mechanical methods, and found to be similar to those previously reported for the beta-3-thienylalanine analogue. The molecular dynamics simulations reveal well-defined folded structures (turn-like) in dilute aqueous solution, driven by self-assembly of the hydrophobic aromatic units, with charged lysine groups exposed to water.

Influence of the solvent on the self-assembly of a modified amyloid beta peptide fragment. II. NMR and computer simulation investigation

The conformation of a model peptide AAKLVFF based on a fragment of the amyloid beta peptide A beta 16-20, KLVFF, is investigated in methanol and water via solution NMR experiments and Molecular dynamics computer simulations. In previous work, we have shown that AAKLVFF forms peptide nanotubes in methanol and twisted fibrils in water. Chemical shift measurements were used to investigate the solubility of the peptide as a function of concentration in methanol and water. This enabled the determination of critical aggregation concentrations, The Solubility was lower in water. In dilute solution, diffusion coefficients revealed the presence of intermediate aggregates in concentrated solution, coexisting with NMR-silent larger aggregates, presumed to be beta-sheets. In water, diffusion coefficients did not change appreciably with concentration, indicating the presence mainly of monomers, coexisting with larger aggregates in more concentrated solution. Concentration-dependent chemical shift measurements indicated a folded conformation for the monomers/intermediate aggregates in dilute methanol, with unfolding at higher concentration. In water, an antiparallel arrangement of strands was indicated by certain ROESY peak correlations. The temperature-dependent solubility of AAKLVFF in methanol was well described by a van't Hoff analysis, providing a solubilization enthalpy and entropy. This pointed to the importance of solvophobic interactions in the self-assembly process. Molecular dynamics Simulations constrained by NOE values from NMR suggested disordered reverse turn structures for the monomer, with an antiparallel twisted conformation for dimers. To model the beta-sheet structures formed at higher concentration, possible model arrangements of strands into beta-sheets with parallel and antiparallel configurations and different stacking sequences were used as the basis for MD simulations; two particular arrangements of antiparallel beta-sheets were found to be stable, one being linear and twisted and the other twisted in two directions. These structures Were used to simulate Circular dichroism spectra. The roles of aromatic stacking interactions and charge transfer effects were also examined. Simulated spectra were found to be similar to those observed experimentally.(in water or methanol) which show a maximum at 215 or 218 nm due to pi-pi* interactions, when allowance is made for a 15-18 nm red-shift that may be due to light scattering effects.

Induced-fit binding of π-electron donor substrates to macrocyclic aromatic ether-imide-sulfones: a versatile approach to molecular assembly

Novel macrocyclic receptors which bind electron-donor aromatic substrates via π-stacking donor- acceptor interactions are obtained by cyclo-imidization of an amine-functionalized arylether-sulfone with pyromellitic- and 1,4,5,8-naphthalene-tetracarboxylic dianhydrides. These macrocycles complex with a wide variety of π-donor substrates including tetrathiafulvalene, naphthalene, anthracene, pyrene, perylene, and functional derivatives of these polycyclic hydrocarbons. The resulting supramolecular assemblies range from simple 1:1 complexes, to [2]- and [3]-pseudorotaxanes, and even (as a result of crystallographic disorder) an apparent polyrotaxane. Direct, five-component self-assembly of a metal-centred [3]pseudorotaxane is also observed, on complexation of a macrocyclic ether-imide with 8-hydroxyquinoline in the presence of palladium(II) ions. Binding studies in solution were carried out by 1H NMR and UV-visible spectroscopy, and the stoichiometries of binding were confirmed by Job plots based on charge-transfer absorption bands. The highest association constants are found for strong π-donor guests with large surface-areas, notably perylene and 1-hydroxypyrene, for which Ka values of 1.4 x 103 and 2.3 x 103 M-1 respectively are found. Single crystal X-ray analyses of the receptors and their derived complexes reveal large, induced-fit distortions of the macrocyclic frameworks as a result of complexation. These structures provide compelling evidence for the existence of strong, attractive forces between the electronically-complementary aromatic π-systems of host and guest.

Sterically controlled recognition of macromolecular sequence information by molecular tweezers

Sequence-specific binding is demonstrated between pyrene-based tweezer molecules and soluble, high molar mass copolyimides. The binding involves complementary pi - pi stacking interactions, polymer chain-folding, and hydrogen bonding and is extremely sensitive to the steric environment around the pyromellitimide binding-site. A detailed picture of the intermolecular interactions involved has been obtained through single-crystal X-ray studies of tweezer complexes with model diimides. Ring-current magnetic shielding of polyimide protons by the pyrene '' arms '' of the tweezer molecule induces large complexation shifts of the corresponding H-1 NMR resonances, enabling specific triplet sequences to be identified by their complexation shifts. Extended comonomer sequences (triplets of triplets in which the monomer residues differ only by the presence or absence of a methyl group) can be '' read '' by a mechanism which involves multiple binding of tweezer molecules to adjacent diimide residues within the copolymer chain. The adjacent-binding model for sequence recognition has been validated by two conceptually different sets of tweezer binding experiments. One approach compares sequence-recognition events for copolyimides having either restricted or unrestricted triple-triplet sequences, and the other makes use of copolymers containing both strongly binding and completely nonbinding diimide residues. In all cases the nature and relative proportions of triple-triplet sequences predicted by the adjacent-binding model are fully consistent with the observed H-1 NMR data.

Adaptive alarm processor for fault diagnosis on power transmission networks

The authors describe a learning classifier system (LCS) which employs genetic algorithms (GA) for adaptive online diagnosis of power transmission network faults. The system monitors switchgear indications produced by a transmission network, reporting fault diagnoses on any patterns indicative of faulted components. The system evaluates the accuracy of diagnoses via a fault simulator developed by National Grid Co. and adapts to reflect the current network topology by use of genetic algorithms.

Real-time expert system for fault location on high voltage underground distribution cables

To ensure minimum loss of system security and revenue it is essential that faults on underground cable systems be located and repaired rapidly. Currently in the UK, the impulse current method is used to prelocate faults, prior to using acoustic methods to pinpoint the fault location. The impulse current method is heavily dependent on the engineer's knowledge and experience in recognising/interpreting the transient waveforms produced by the fault. The development of a prototype real-time expert system aid for the prelocation of cable faults is described. Results from the prototype demonstrate the feasibility and benefits of the expert system as an aid for the diagnosis and location of faults on underground cable systems.