Segregated self-assembly and pillaring action of aliphatic dicarboxylic acids in the super structure of Cu-picolinate complexes

Three new supramolecular assemblies of co-crystallized metal complexes and aliphatic dicarboxylic acids, {[Cu(pic)(2)(H2O)(2)](H(2)mal)}(n) (1), {[Cu(pic)(2)(H2O)(2)](H(2)mal)(2)(H2O)(2)}(n) (2) and {[Cu(pic)(2)(MeOH)](H(2)succ)}(n) (3) {Hpic = 2-picolinic acid, H(2)mal = malonic acid and H(2)succ = succinic acid} have been synthesized and characterized by X-ray single-crystal structure determination. The crystal packings of the complexes reveal that supramolecular associations of the monomeric complex units lead to the formation of layers through hydrogen bonding. In all the complexes, the dicarboxylic acid units connect the 2-D layers to act as pillars. The interaction between water molecules and the dicarboxylic acid plays an important role in the overall supramolecular assembly. (C) 2008 Elsevier Ltd. All rights reserved.

Zinc(II)-pyridylthioazophenol system: synthesis, characterization and crystal structure

Reactivities of pyridylthioazophenols (1) with zinc(II) salts have been studied and the complexes isolated in pure form and characterized. Pyridylthioazophenols react with zinc( II)acetate in MeOH/EtOH at room temperature to give a series of pyridylsulfinylazophenols (2)but no zinc( II) complex. The sulfoxides (2) have been characterized by IR and NMR. One of the pyridylsulfinylazophenols (2a) has been subjected to single-crystal X-ray analysis in order to confirm details of its structure. A series of dimeric zinc( II) complexes of tetradentate NSNO pyridylthioazophenolates has been isolated through reaction of zinc nitrate in MeOH followed by in situ reaction with azide ion, which acts as a mu-(1,1) bridge. All complexes have been characterized spectroscopically. The detailed structure of one of the dinuclear zinc( II) complexes has been established by a single-crystal X-ray structure determination. In complex 3a two octahedrally coordinated zinc( II) ions are bridged by two end-on azide ions. No reactions of pyridylthioazophenols with zinc chloride in refluxing EtOH have been observed.

Two new mu-(1,3-azido)-bridged polymers: alternating single and double bridges in a 1D nickel(II) complex and uniform bridge in a 2D copper(II) complex: Syntheses, single-crystal structures and magnetic studies

Two polymeric azido bridged complexes [Ni2L2(N-3)(3)](n)(ClO4). (1) and [Cu(bpdS)(2)(N-3)],(ClO4),(H2O)(2.5n) (2) [L = Schiff base, obtained from the condensation of pyridine-2-aldehyde with N,N,2,2-tetramethyl-1,3-propanediamine; bpds = 4,4'-bipyridyl disulfide] have been synthesized and their crystal structures have been determined. Complex 1, C26H42ClN15Ni2O4, crystallizes in a triclinic system, space group P1 with a 8.089(13), b = 9.392(14), c = 12.267(18) angstrom, a = 107.28(l), b 95.95(1), gamma = 96.92(1)degrees and Z = 2; complex 2, C20H21ClCuN7O6.5S4, crystallizes in an orthorhombic system, space group Pnna with a = 10.839(14), b = 13.208(17), c = 19.75(2) angstrom and Z = 4. The crystal structure of I consists of 1D polymers of nickel(L) units, alternatively connected by single and double bridging mu-(1,3-N-3) ligand with isolated perchlorate anions. Variable temperature magnetic susceptibility data of the complex have been measured and the fitting,of magnetic data was carried out applying the Borris-Almenar formula for such types of alternating one-dimensional S = 1 systems, based on the Hamiltonian H = -J Sigma(S2iS2i-1 + aS(2i)S(2i+1)). The best-fit parameters obtained are J = -106.7 +/- 2 cm(-1); a = 0.82 +/- 0.02; g = 2.21 +/- 0.02. Complex 2 is a 2D network of 4,4 topology with the nodes occupied by the Cu-II ions, and the edges formed by single azide and double bpds connectors. The perchlorate anions are located between pairs of bpds. The magnetic data have been fitted considering the complex as a pseudo-one-dimensional system, with all copper((II)) atoms linked by [mu(1,3-azido) bridging ligands at axial positions (long Cu...N-3 distances) since the coupling through long bpds is almost nil. The best-fit parameters obtained with this model are J = -1.21 +/- 0.2 cm(-1), g 2.14 +/- 0.02. (c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005).

Synthesis, structure and properties of cobalt(II/III) seleno-bisphenolate complexes containing NN bidentate co-ligands: kinetic studies on the reduction of a cobalt(III) complex by ascorbic acid in 80% MeCN-20% water

Two cobalt complexes, [Co(L-Se)(phen)]center dot CH2Cl2 (1) and [Co(L-Se)(N,N-Me(2)en)(CH3COO-)] (2) have been synthesized and characterized by elemental analyses, magnetic measurements, i.r. studies etc. Single crystal X- ray studies reveal that in complex (1) cobalt atom is in +2 oxidation state with trigonal bipyramidal geometry, while in complex (2) it is in +3 oxidation state and surrounded octahedrally. The asymmetric unit of complex (2) contains two crystallographically independent discrete molecules. Complex (1) was found to be paramagnetic with mu(eff) = 2.19 BM indicating a low spin cobalt(II) d(7) system, whereas complex (2) is found to be diamagnetic with cobalt(III) in low spin d(6) state. The kinetic studies on the reduction of (2) by ascorbic acid in 80% MeCN-20% H2O (v/v) at 25 degrees C reveal that the reaction proceeds through the rapid formation of inner-sphere adduct, probably by replacing the loosely coordinated AcO- group, followed by electron transfer in a slow step and is supported by a large Q (formation constant) value.

Mapping fibre orientation in complex-shaped biological systems with micrometre resolution by scanning X-ray microdiffraction

A fully automated procedure to extract and to image local fibre orientation in biological tissues from scanning X-ray diffraction is presented. The preferred chitin fibre orientation in the flow sensing system of crickets is determined with high spatial resolution by applying synchrotron radiation based X-ray microbeam diffraction in conjunction with advanced sample sectioning using a UV micro-laser. The data analysis is based on an automated detection of azimuthal diffraction maxima after 2D convolution filtering (smoothing) of the 2D diffraction patterns. Under the assumption of crystallographic fibre symmetry around the morphological fibre axis, the evaluation method allows mapping the three-dimensional orientation of the fibre axes in space. The resulting two-dimensional maps of the local fibre orientations - together with the complex shape of the flow sensing system - may be useful for a better understanding of the mechanical optimization of such tissues.

Truth in complex adaptive systems models should be based on truth by constructive verification

It is argued that the truth status of emergent properties of complex adaptive systems models should be based on an epistemology of proof by constructive verification and therefore on the ontological axioms of a non-realist logical system such as constructivism or intuitionism. ‘Emergent’ properties of complex adaptive systems (CAS) models create particular epistemological and ontological challenges. These challenges bear directly on current debates in the philosophy of mathematics and in theoretical computer science. CAS research, with its emphasis on computer simulation, is heavily reliant on models which explore the entailments of Formal Axiomatic Systems (FAS). The incompleteness results of Gödel, the incomputability results of Turing, and the Algorithmic Information Theory results of Chaitin, undermine a realist (platonic) truth model of emergent properties. These same findings support the hegemony of epistemology over ontology and point to alternative truth models such as intuitionism, constructivism and quasi-empiricism.

Modelling the interdependence between the stoichiometry of receptor oligomerization and ligand binding for a coexisting dimer/tetramer receptor system

Many G protein-coupled receptors have been shown to exist as oligomers, but the oligomerization state and the effects of this on receptor function are unclear. For some G protein-coupled receptors, in ligand binding assays, different radioligands provide different maximal binding capacities. Here we have developed mathematical models for co-expressed dimeric and tetrameric species of receptors. We have considered models where the dimers and tetramers are in equilibrium and where they do not interconvert and we have also considered the potential influence of the ligands on the degree of oligomerization. By analogy with agonist efficacy, we have considered ligands that promote, inhibit or have no effect on oligomerization. Cell surface receptor expression and the intrinsic capacity of receptors to oligomerize are quantitative parameters of the equations. The models can account for differences in the maximal binding capacities of radioligands in different preparations of receptors and provide a conceptual framework for simulation and data fitting in complex oligomeric receptor situations.

Mechanisms of inverse agonist action at D-2 dopamine receptors

1 Mechanisms of inverse agonist action at the D-2(short) dopamine receptor have been examined. 2 Discrimination of G-protein-coupled and -uncoupled forms of the receptor by inverse agonists was examined in competition ligand-binding studies versus the agonist [H-3]NPA at a concentration labelling both G-protein-coupled and -uncoupled receptors. 3 Competition of inverse agonists versus [H-3] NPA gave data that were fitted best by a two-binding site model in the absence of GTP but by a one-binding site model in the presence of GTP. K-i values were derived from the competition data for binding of the inverse agonists to G-protein-uncoupled and -coupled receptors. K-coupled and K-uncoupled were statistically different for the set of compounds tested ( ANOVA) but the individual values were different in a post hoc test only for (+)-butaclamol. 4 These observations were supported by simulations of these competition experiments according to the extended ternary complex model. 5 Inverse agonist efficacy of the ligands was assessed from their ability to reduce agonist-independent [S-35]GTPγ S binding to varying degrees in concentration-response curves. Inverse agonism by (+)-butaclamol and spiperone occurred at higher potency when GDP was added to assays, whereas the potency of (-)-sulpiride was unaffected. 6 These data show that some inverse agonists ((+)-butaclamol, spiperone) achieve inverse agonism by stabilising the uncoupled form of the receptor at the expense of the coupled form. For other compounds tested, we were unable to define the mechanism.

Liposomes and skin: From drug delivery to model membranes

The early eighties saw the introduction of liposomes as skin drug delivery systems, initially promoted primarily for localised effects with minimal systemic delivery. Subsequently, a novel ultradeformable vesicular system (termed "Transfersomes" by the inventors) was reported for transdermal delivery with an efficiency similar to subcutaneous injection. Further research illustrated that the mechanisms of liposome action depended on the application regime and the vesicle composition and morphology. Ethical, health and supply problems with human skin have encouraged researchers to use skin models. 'IYaditional models involved polymer membranes and animal tissue, but whilst of value for release studies, such models are not always good mimics for the complex human skin barrier, particularly with respect to the stratum corneal intercellular lipid domains. These lipids have a multiply bilayered organization, a composition and organization somewhat similar to liposomes, Consequently researchers have used vesicles as skin model membranes. Early work first employed phospholipid liposomes and tested their interactions with skin penetration enhancers, typically using thermal analysis and spectroscopic analyses. Another approach probed how incorporation of compounds into liposomes led to the loss of entrapped markers, analogous to "fluidization" of stratum corneum lipids on treatment with a penetration enhancer. Subsequently scientists employed liposomes formulated with skin lipids in these types of studies. Following a brief description of the nature of the skin barrier to transdermal drug delivery and the use of liposomes in drug delivery through skin, this article critically reviews the relevance of using different types of vesicles as a model for human skin in permeation enhancement studies, concentrating primarily on liposomes after briefly surveying older models. The validity of different types of liposome is considered and traditional skin models are compared to vesicular model membranes for their precision and accuracy as skin membrane mimics. (c) 2008 Elsevier B.V. All rights reserved.

Determining feature relevance for the grouping of motor unit action potentials through generative topographic mapping

The study of motor unit action potential (MUAP) activity from electrornyographic signals is an important stage on neurological investigations that aim to understand the state of the neuromuscular system. In this context, the identification and clustering of MUAPs that exhibit common characteristics, and the assessment of which data features are most relevant for the definition of such cluster structure are central issues. In this paper, we propose the application of an unsupervised Feature Relevance Determination (FRD) method to the analysis of experimental MUAPs obtained from healthy human subjects. In contrast to approaches that require the knowledge of a priori information from the data, this FRD method is embedded on a constrained mixture model, known as Generative Topographic Mapping, which simultaneously performs clustering and visualization of MUAPs. The experimental results of the analysis of a data set consisting of MUAPs measured from the surface of the First Dorsal Interosseous, a hand muscle, indicate that the MUAP features corresponding to the hyperpolarization period in the physisiological process of generation of muscle fibre action potentials are consistently estimated as the most relevant and, therefore, as those that should be paid preferential attention for the interpretation of the MUAP groupings.

Requirements analysis for an e-government system to support multi-organisational collaborative groups

We present a conceptual architecture for a Group Support System (GSS) to facilitate Multi-Organisational Collaborative Groups (MOCGs) initiated by local government and including external organisations of various types. Multi-Organisational Collaborative Groups (MOCGs) consist of individuals from several organisations which have agreed to work together to solve a problem. The expectation is that more can be achieved working in harmony than separately. Work is done interdependently, rather than independently in diverse directions. Local government, faced with solving complex social problems, deploy MOCGs to enable solutions across organisational, functional, professional and juridical boundaries, by involving statutory, voluntary, community, not-for-profit and private organisations. This is not a silver bullet as it introduces new pressures. Each member organisation has its own goals, operating context and particular approaches, which can be expressed as their norms and business processes. Organisations working together must find ways of eliminating differences or mitigating their impact in order to reduce the risks of collaborative inertia and conflict. A GSS is an electronic collaboration system that facilitates group working and can offer assistance to MOCGs. Since many existing GSSs have been primarily developed for single organisation collaborative groups, even though there are some common issues, there are some difficulties peculiar to MOCGs, and others that they experience to a greater extent: a diversity of primary organisational goals among members; different funding models and other pressures; more significant differences in other information systems both technologically and in their use than single organisations; greater variation in acceptable approaches to solve problems. In this paper, we analyse the requirements of MOCGs led by local government agencies, leading to a conceptual architecture for an e-government GSS that captures the relationships between 'goal', 'context', 'norm', and 'business process'. Our models capture the dynamics of the circumstances surrounding each individual representing an organisation in a MOCG along with the dynamics of the MOCG itself as a separate community.

Semiotic modelling for complex enterprise systems

An enterprise is viewed as a complex system which can be engineered to accomplish organisational objectives. Systems analysis and modelling will enable to the planning and development of the enterprise and IT systems. Many IT systems design methods focus on functional and non-functional requirements of the IT systems. Most methods are normally capable of one but leave out other aspects. Analysing and modelling of both business and IT systems may often have to call on techniques from various suites of methods which may be placed on different philosophic and methodological underpinnings. Coherence and consistency between the analyses are hard to ensure. This paper introduces the Problem Articulation Method (PAM) which facilitates the design of an enterprise system infrastructure on which an IT system is built. Outcomes of this analysis represent requirements which can be further used for planning and designing a technical system. As a case study, a finance system, Agresso, for e-procurement has been used in this paper to illustrate the applicability of PAM in modelling complex systems.

Apodisation, denoising and system identification techniques for THz transients in the wavelet domain

This work describes the use of a quadratic programming optimization procedure for designing asymmetric apodization windows to de-noise THz transient interferograms and compares these results to those obtained when wavelet signal processing algorithms are adopted. A systems identification technique in the wavelet domain is also proposed for the estimation of the complex insertion loss function. The proposed techniques can enhance the frequency dependent dynamic range of an experiment and should be of particular interest to the THz imaging and tomography community. Future advances in THz sources and detectors are likely to increase the signal-to-noise ratio of the recorded THz transients and high quality apodization techniques will become more important, and may set the limit on the achievable accuracy of the deduced spectrum.

3D path planning with novel multiple 2D layered approach for complex human-robot interaction

Navigating cluttered indoor environments is a difficult problem in indoor service robotics. The Acroboter concept, a novel approach to indoor locomotion, represents unique opportunity to avoid obstacles in indoor environments by navigating the ceiling plane. This mode of locomotion requires the ability to accurately detect obstacles, and plan 3D trajectories through the environment. This paper presents the development of a resilient object tracking system, as well as a novel approach to generating 3D paths suitable for such robot configurations. Distributed human-machine interfacing allowing simulation previewing of actions is also considered in the developed system architecture.

Managing groups of files in a rule oriented data management system (iRODS)

The iRODS system, created by the San Diego Supercomputing Centre, is a rule oriented data management system that allows the user to create sets of rules to define how the data is to be managed. Each rule corresponds to a particular action or operation (such as checksumming a file) and the system is flexible enough to allow the user to create new rules for new types of operations. The iRODS system can interface to any storage system (provided an iRODS driver is built for that system) and relies on its’ metadata catalogue to provide a virtual file-system that can handle files of any size and type. However, some storage systems (such as tape systems) do not handle small files efficiently and prefer small files to be packaged up (or “bundled”) into larger units. We have developed a system that can bundle small data files of any type into larger units - mounted collections. The system can create collection families and contains its’ own extensible metadata, including metadata on which family the collection belongs to. The mounted collection system can work standalone and is being incorporated into the iRODS system to enhance the systems flexibility to handle small files. In this paper we describe the motivation for creating a mounted collection system, its’ architecture and how it has been incorporated into the iRODS system. We describe different technologies used to create the mounted collection system and provide some performance numbers.