The interplay of secondary Hg⋯S, Hg⋯N and Hg⋯π bonding interactions in supramolecular structures of phenylmercury(ii) dithiocarbamates

Three new phenylmercury(II) and one mercury(II) dithiocarbamate complexes viz. PhHg S2CN(PyCH2) Bz (1), PhHg S2CN(PyCH2)CH3 (2), PhHg S2CN(Bz)CH3 (3), and [Hg (NCS2(PyCH2)Bz)(2)] (4) (Py = pyridine; Bz = benzyl) have been synthesized and characterized by elemental analyses, IR, electronic absorption, H-1 and C-13 NMR spectroscopy. The crystal structures of 1, 2 and 3 showed a linear S-Hg-C core at the centre of the molecule, in which the metal atom is bound to the sulfur atom of the dithiocarbamate ligand and a carbon atom of the aromatic ring. In contrast the crystal structure of 4 showed a linear S-Hg-S core at the Hg(II) centre of the molecule. Weak intermolecular Hg center dot center dot center dot N (Py) interactions link molecules into a linear chain in the case of 1, whereas chains of dimers are formed in 2 through intermolecular Hg center dot center dot center dot N (Py) and Hg center dot center dot center dot S interactions. 3 forms a conventional face-to-edge dimeric structure through intermolecular Hg center dot center dot center dot S secondary bonding and 4 forms a linear chain of dimers through face-to-face Hg center dot center dot center dot S secondary bonding. In order to elucidate the nature of these secondary bonding interactions and the electronic absorption spectra of the complexes, ab initio quantum chemical calculations at the MP2 level and density functional theory calculations were carried out for 1-3. Complexes 1 and 2 exhibited photoluminescent properties in the solid state as well as in the solution phase. Studies indicate that Hg center dot center dot center dot S interactions decrease and Hg center dot center dot center dot N interactions increase the chances of photoluminescence in the solid phase

An organisational semiotics inspired information architecture: pervasive healthcare as a case study

Information architecture (IA) is defined as high level information requirements of an organisation. It is applied in areas such as information systems development, enterprise architecture, business processes management and organisational change management. Still, the lack of methods and theories prevents information architecture becoming a distinct discipline. Healthcare organisation is always seen as information intensive organisation, moreover in a pervasive healthcare environment. Pervasive healthcare aims to provide healthcare services to anyone, anywhere and anytime by incorporating mobile devices and wireless network. Information architecture hence plays an important role in information provisioning within the context of pervasive healthcare in order to support decision making and communication between clinician and patients. Organisational semiotics is one of the social technical approaches that contemplate information through the norms or activities performed within an organisation prior to pervasive healthcare implementation. This paper proposes a conceptual design of information architecture for pervasive healthcare. It is illustrated with a scenario of mental health patient monitoring.

Parallel pipelined histogram architecture via c-slow retiming

A parallel pipelined array of cells suitable for realtime computation of histograms is proposed. The cell architecture builds on previous work to now allow operating on a stream of data at 1 pixel per clock cycle. This new cell is more suitable for interfacing to camera sensors or to microprocessors of 8-bit data buses which are common in consumer digital cameras. Arrays using the new proposed cells are obtained via C-slow retiming techniques and can be clocked at a 65% faster frequency than previous arrays. This achieves over 80% of the performance of two-pixel per clock cycle parallel pipelined arrays.

A parallel quantum histogram architecture

A parallel formulation of an algorithm for the histogram computation of n data items using an on-the-fly data decomposition and a novel quantum-like representation (QR) is developed. The QR transformation separates multiple data read operations from multiple bin update operations thereby making it easier to bind data items into their corresponding histogram bins. Under this model the steps required to compute the histogram is n/s + t steps, where s is a speedup factor and t is associated with pipeline latency. Here, we show that an overall speedup factor, s, is available for up to an eightfold acceleration. Our evaluation also shows that each one of these cells requires less area/time complexity compared to similar proposals found in the literature.

Healable supramolecular polymeric materials

This chapter details the design, synthesis and evaluation techniques required to produce healable supramolecular materials. Key developments in supramolecular polymer chemistry that laid down the design concepts necessary to produce responsive materials are summarized. Subsequently, select examples from the literature concerning the synthesis and analysis of healable materials containing hydrogen bonding, π−π stacking and metal–ligand interactions are evaluated. The last section describes the most recent efforts to produce healable gels for niche applications, including electrolytes and tissue engineering scaffolds. The chapter also describes the design criteria and production of nano-composite materials that exhibit dramatically increased strength compared to previous generations of supramolecular materials, whilst still retaining the key healing characteristics.

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.

Integrated clinical pathway management for medical quality improvement-based on a semiotically inspired systems architecture

Clinical pathway is an approach to standardise care processes to support the implementations of clinical guidelines and protocols. It is designed to support the management of treatment processes including clinical and non-clinical activities, resources and also financial aspects. It provides detailed guidance for each stage in the management of a patient with the aim of improving the continuity and coordination of care across different disciplines and sectors. However, in the practical treatment process, the lack of knowledge sharing and information accuracy of paper-based clinical pathways burden health-care staff with a large amount of paper work. This will often result in medical errors, inefficient treatment process and thus poor quality medical services. This paper first presents a theoretical underpinning and a co-design research methodology for integrated pathway management by drawing input from organisational semiotics. An approach to integrated clinical pathway management is then proposed, which aims to embed pathway knowledge into treatment processes and existing hospital information systems. The capability of this approach has been demonstrated through the case study in one of the largest hospitals in China. The outcome reveals that medical quality can be improved significantly by the classified clinical pathway knowledge and seamless integration with hospital information systems.

Portfolio advertising as an instrument to strengthen the corporate brand in a complex brand architecture

In recent years, the importance of the corporate brand has significantly grown and companies increasingly seek to strengthen their corporate brand. The corporate brand image can be strengthened through portfolio advertising as a technique of impression management. This mechanism works only if important variables are considered, such as the fit between product brands, the number of product brands as well as the processing depth of the consumers. Based on three experiments, the benefits of portfolio advertising for the corporate brand and its product brands are shown and practical implications are discussed.

Molecular recognition between functionalized gold nanoparticles and healable, supramolecular polymer blends – a route to property enhancement

A new, healable, supramolecular nanocomposite material has been developed and evaluated. The material comprises a blend of three components: a pyrene-functionalized polyamide, a polydiimide and pyrenefunctionalized gold nanoparticles (P-AuNPs). The polymeric components interact by forming well-defined p–p stacked complexes between p-electron rich pyrenyl residues and p-electron deficient polydiimide residues. Solution studies in the mixed solvent chloroform–hexafluoroisopropanol (6 : 1, v/v) show that mixing the three components (each of which is soluble in isolation), results in the precipitation of a supramolecular, polymer nanocomposite network. The precipitate thus formed can be re-dissolved on heating, with the thermoreversible dissolution/precipitation procedure repeatable over at least 5 cycles. Robust, self-supporting composite films containing up to 15 wt% P-AuNPs could be cast from 2,2,2- trichloroethanol. Addition of as little as 1.25 wt% P-AuNPs resulted in significantly enhanced mechanical properties compared to the supramolecular blend without nanoparticles. The nanocomposites showed a linear increase in both tensile moduli and ultimate tensile strength with increasing P-AuNP content. All compositions up to 10 wt% P-AuNPs exhibited essentially quantitative healing efficiencies. Control experiments on an analogous nanocomposite material containing dodecylamine-functionalized AuNPs (5 wt%) exhibited a tensile modulus approximately half that of the corresponding nanocomposite that incorporated 5 wt% pyrene functionalized-AuNPs, clearly demonstrating the importance of the designed interactions between the gold filler and the supramolecular polymer matrix.

Healable supramolecular polymers

This mini-review details the recent development of self-healing and mendable polymeric materials which take advantage of the reversible characteristics of non-covalent interactions during their physical recovery process. Supramolecular polymer systems which undergo spontaneous (autonomous) healing, as well as those which require external stimuli to initiate the healing process (healable/mendable), are introduced and discussed. Supramolecular polymers offer key advantages over alternative approaches, as these materials can typically withstand multiple healing cycles without substantial loss of performance, as a consequence of the highly directional and fully reversible non-covalent interactions present within the polymer matrix.

Shoot yield drives phosphorus use efficiency in Brassica oleracea and correlates with root architecture traits

The environmental and financial costs of using inorganic phosphate fertilizers to maintain crop yield and quality are high. Breeding crops that acquire and use phosphorus (P) more efficiently could reduce these costs. The variation in shoot P concentration (shoot-P) and various measures of P use efficiency (PUE) were quantified among 355 Brassica oleracea L. accessions, 74 current commercial cultivars, and 90 doubled haploid (DH) mapping lines from a reference genetic mapping population. Accessions were grown at two or more external P concentrations in glasshouse experiments; commercial and DH accessions were also grown in replicated field experiments. Within the substantial species-wide diversity observed for shoot-P and various measures of PUE in B. oleracea, current commercial cultivars have greater PUE than would be expected by chance. This may be a consequence of breeding for increased yield, which is a significant component of most measures of PUE, or early establishment. Root development and architecture correlate with PUE; in particular, lateral root number, length, and growth rate. Significant quantitative trait loci associated with shoot-P and PUE occur on chromosomes C3 and C7. These data provide information to initiate breeding programmes to improve PUE in B. oleracea.

A benchmark-driven modelling approach for evaluating deployment choices on a multicore architecture

The complexity of current and emerging high performance architectures provides users with options about how best to use the available resources, but makes predicting performance challenging. In this work a benchmark-driven performance modelling approach is outlined that is appro- priate for modern multicore architectures. The approach is demonstrated by constructing a model of a simple shallow water code on a Cray XE6 system, from application-specific benchmarks that illustrate precisely how architectural char- acteristics impact performance. The model is found to recre- ate observed scaling behaviour up to 16K cores, and used to predict optimal rank-core affinity strategies, exemplifying the type of problem such a model can be used for.

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.