Host–guest supramolecular interactions in the coordination compounds of 4,4′-azobis(pyridine) with MnX2(X = NCS–, NCNCN–, and PF6–): structural analyses and theoretical study

Three new Mn(II) coordination compounds {[Mn(NCNCN)2(azpy)]·0.5azpy}n (1), {[Mn(NCS)2(azpy)(CH3OH)2]·azpy}n (2), and [Mn(azpy)2(H2O)4][Mn(azpy)(H2O)5]·4PF6·H2O·5.5azpy (3) (where azpy = 4,4'-azobis-(pyridine)) have been synthesized by self-assembly of the primary ligands, dicyanamide, thiocyanate, and hexafluorophosphate, respectively, together with azpy as the secondary spacer. All three complexes were characterized by elemental analyses, IR spectroscopy, thermal analyses, and single crystal X-ray crystallography. The structural analyses reveal that complex 1 forms a two-dimensional (2D) grid sheet motif These sheets assemble to form a microporous framework that incorporates coordination-free azpy by host-guest pi center dot center dot center dot pi. and C-H center dot center dot center dot N hydrogen bonding interactions. Complex 2 features azpy bridged one-dimensional (ID) chains of centrosymmetric [Mn(NCS)(2)(CH3OH)(2)} units which form a 2D porous sheet via a CH3 center dot center dot center dot pi supramolecular interaction. A guest azpy molecule is incorporated within the pores by strong H-bonding interactions. Complex 3 affords a 0-D motif with two monomeric Mn(II) units in the asymmetric unit. There exist pi center dot center dot center dot pi, anion center dot center dot center dot pi, and strong hydrogen bonding interactions between the azpy, water, and the anions. Density functional theory (DFT) calculations, at the M06/6-31+G* level of theory, are used to characterize a great variety of interactions that explicitly show the importance of host-guest supramolecular interactions for the stabilization of coordination compounds and creation of the fascinating three-dimensional (3D) architecture of the title compounds.

A Web Map Service implementation for the visualization of multidimensional gridded environmental data

We describe ncWMS, an implementation of the Open Geospatial Consortium’s Web Map Service (WMS) specification for multidimensional gridded environmental data. ncWMS can read data in a large number of common scientific data formats – notably the NetCDF format with the Climate and Forecast conventions – then efficiently generate map imagery in thousands of different coordinate reference systems. It is designed to require minimal configuration from the system administrator and, when used in conjunction with a suitable client tool, provides end users with an interactive means for visualizing data without the need to download large files or interpret complex metadata. It is also used as a “bridging” tool providing interoperability between the environmental science community and users of geographic information systems. ncWMS implements a number of extensions to the WMS standard in order to fulfil some common scientific requirements, including the ability to generate plots representing timeseries and vertical sections. We discuss these extensions and their impact upon present and future interoperability. We discuss the conceptual mapping between the WMS data model and the data models used by gridded data formats, highlighting areas in which the mapping is incomplete or ambiguous. We discuss the architecture of the system and particular technical innovations of note, including the algorithms used for fast data reading and image generation. ncWMS has been widely adopted within the environmental data community and we discuss some of the ways in which the software is integrated within data infrastructures and portals.

'Quasi'-norm of an arithmetical convolution operator and the order of the Riemann zeta function

In this paper we study Dirichlet convolution with a given arithmetical function f as a linear mapping 'f that sends a sequence (an) to (bn) where bn = Pdjn f(d)an=d. We investigate when this is a bounded operator on l2 and ¯nd the operator norm. Of particular interest is the case f(n) = n¡® for its connection to the Riemann zeta function on the line 1, 'f is bounded with k'f k = ³(®). For the unbounded case, we show that 'f : M2 ! M2 where M2 is the subset of l2 of multiplicative sequences, for many f 2 M2. Consequently, we study the `quasi'-norm sup kak = T a 2M2 k'fak kak for large T, which measures the `size' of 'f on M2. For the f(n) = n¡® case, we show this quasi-norm has a striking resemblance to the conjectured maximal order of j³(® + iT )j for ® > 12 .

Modeling requirement driven architecture of adaptive healthcare system based on semiotics

In order to improve the quality of healthcare services, the integrated large-scale medical information system is needed to adapt to the changing medical environment. In this paper, we propose a requirement driven architecture of healthcare information system with hierarchical architecture. The system operates through the mapping mechanism between these layers and thus can organize functions dynamically adapting to user’s requirement. Furthermore, we introduce the organizational semiotics methods to capture and analyze user’s requirement through ontology chart and norms. Based on these results, the structure of user’s requirement pattern (URP) is established as the driven factor of our system. Our research makes a contribution to design architecture of healthcare system which can adapt to the changing medical environment.

Thinking out of the box – skills for work

Since the Dearing Report .1 there has been an increased emphasis on the development of employability and transferable (‘soft’) skills in undergraduate programmes. Within STEM subject areas, recent reports concluded that universities should offer ‘greater and more sustainable variety in modes of study to meet the changing demands of industry and students’.2 At the same time, higher education (HE) institutions are increasingly conscious of the sensitivity of league table positions on employment statistics and graduate destinations. Modules that are either credit or non-credit bearing are finding their way into the core curriculum at HE. While the UK government and other educational bodies argue the way forward over A-level reform, universities must also meet the needs of their first year cohorts in terms of the secondary to tertiary transition and developing independence in learning.

Self-assembly and bioactivity of a polymer/peptide conjugate containing the RGD cell adhesion motif and PEG

The self-assembly and bioactivity of the peptide–polymer conjugate DGRFFF–PEG3000 containing the RGD cell adhesion motif has been examined, in aqueous solution. The conjugate is designed to be amphiphilic by incorporation of three hydrophobic phenylalanine residues as well as the RGD unit and a short poly(ethylene glycol) (PEG) chain of molar mass 3000 kg mol-1. Above a critical aggregation concentration, determined by fluorescence measurements, signals of b-sheet structure are revealed by spectroscopic measurements, as well as X-ray diffraction. At high concentration, a self-assembled fibril nanostructure is revealed by electron microscopy. The fibrils are observed despite PEG crystallization which occurs on drying. This suggests that DGRFFF has an aggregation tendency that is sufficiently strong not to be prevented by PEG crystallization. The adhesion, viability and proliferation of human corneal fibroblasts was examined for films of the conjugate on tissue culture plates (TCPs) as well as low attachment plates. On TCP, DGRFFF–PEG3000 films prepared at sufficiently low concentration are viable, and cell proliferation is observed. However, on low attachment surfaces, neither cell adhesion nor proliferation was observed, indicating that the RGD motif was not available to enhance cell adhesion. This was ascribed to the core–shell architecture of the self-assembled fibrils with a peptide core surrounded by a PEG shell which hinders access to the RGD unit.

GridRM: a resource monitoring architecture for the grid

Monitoring resources is an important aspect of the overall efficient usage and control of any distributed system. In this paper, we describe a generic open-source resource monitoring architecture that has been specifically designed for the Grid. The paper consists of three main sections. In the first section, we outline our motivation and briefly detail similar work in the area. In the second section, we describe the general monitoring architecture and its components. In the final section of the paper, we summarise the experiences so far and outline our future work.

The historic landscape of the Mendip Hills

When travelling north-east across the Somerset Levels and Moors the eye is drawn to the dark mass of the Mendip Hills, a Carboniferous Limestone ridge which rises abruptly from the flatness of its surroundings. The Historic Landscape of the Mendip Hills explores the archaeology and architecture of this remarkable corner of England, beginning with evidence for the first hunting groups who passed through the region over half a million years ago. Succeeding generations have left their mark on the Hills, from the enigmatic ceremonial structures of the Neolithic and Early Bronze Age, to the ancient farming landscapes and brooding hillforts of the Later Prehistoric period. Field archaeology, combined with architectural and historical enquiry, has also allowed a complex narrative to be constructed for more recent periods of history. This is a story dominated by adaptation and change, evidenced by the developing architecture of manorial centres and the shadowy remains of earlier structures fossilized within village houses. This volume presents a synthesis of the results of recent fieldwork undertaken by English Heritage and traces this region’s remarkable past, revealing ways in which it has shaped the landscape we see and value today.

Aesthetical and narrative uses of the trench in the Hollywood cinema of 1918-1930

Throughout history of painting, the representation of landscape has been considered a laboratory for the human gaze on the world. The First World War and its new approach to the battlefield altered deeply the classical forms of representation, and replaced them with a mechanised and fragmentary vision, which was related with the development of photography and cinema. As Vicente J. Benet has analysed, Hollywod cinema used these deep changes in its filmic versions of the conflict, although it organised them following a narrative logic. In this text we intend to study how the battlefield and, particularly, the trench, are inserted in this logic of the history of landscape painting. We do so through some Hollywood films from the period 1918-1930. Firstly, we approach the trench as a composition value which can structure the image and guide the camera movement. In the second place, we study how it creates a dialog between its inside, melodrama scenery, and the outside, battlefield and danger. In both cases, we conclude that the trench as a form and as a narrative element plays a structuring and integrative role with the storytelling logic.