Homo- and heteronuclear meso,meso-(E)-Ethene-1,2-diyl-Linked Diporphyrins : preparation, X-ray crystal structure, electronic absorption and emission spectra and density functional theory calculations

Homo-and heteronuclear meso,meso-(E)-ethene-1,2-diyl-linked diporphyrins have been prepared by the Suzuki coupling of porphyrinylboronates and iodovinylporphyrins. Combinations comprising 5,10,15-triphenylporphyrin (TriPP) on both ends of the ethene-1,2-diyl bridge M 210 (M 2=H 2/Ni, Ni 2, Ni/Zn, H 4, H 2Zn, Zn 2) and 5,15-bis(3,5-di-tert-butylphenyl)porphyrinato-nickel(II) on one end and H 2, Ni, and ZnTriPP on the other (M 211), enable the first studies of this class of compounds possessing intrinsic polarity. The compounds were characterized by electronic absorption and steady state emission spectra, 1H NMR spectra, and for the Ni 2 bis(TriPP) complex Ni 210, single crystal X-ray structure determination. The crystal structure shows ruffled distortions of the porphyrin rings, typical of Ni II porphyrins, and the (E)-C 2H 2 bridge makes a dihedral angle of 50° with the mean planes of the macrocycles. The result is a stepped parallel arrangement of the porphyrin rings. The dihedral angles in the solid state reflect the interplay of steric and electronic effects of the bridge on interporphyrin communication. The emission spectra in particular, suggest energy transfer across the bridge is fast in conformations in which the bridge is nearly coplanar with the rings. Comparisons of the fluorescence behaviour of H 410 and H 2Ni10 show strong quenching of the free base fluorescence when the complex is excited at the lower energy component of the Soret band, a feature associated in the literature with more planar conformations. TDDFT calculations on the gas-phase optimized geometry of Ni 210 reproduce the features of the experimental electronic absorption spectrum within 0.1 eV. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Scalability of encryption techniques for electronic health record (EHR) retrieval

Electronic Health Record (EHR) retrieval processes are complex demanding Information Technology (IT) resources exponentially in particular memory usage. Database-as-a-service (DAS) model approach is proposed to meet the scalability factor of EHR retrieval processes. A simulation study using ranged of EHR records with DAS model was presented. The bucket-indexing model incorporated partitioning fields and bloom filters in a Singleton design pattern were used to implement custom database encryption system. It effectively provided faster responses in the range query compared to different types of queries used such as aggregation queries among the DAS, built-in encryption and the plain-text DBMS. The study also presented with constraints around the approach should consider for other practical applications.

Semantic service discovery in the service ecosystem

Electronic services are a leitmotif in ‘hot’ topics like Software as a Service, Service Oriented Architecture (SOA), Service oriented Computing, Cloud Computing, application markets and smart devices. We propose to consider these in what has been termed the Service Ecosystem (SES). The SES encompasses all levels of electronic services and their interaction, with human consumption and initiation on its periphery in much the same way the ‘Web’ describes a plethora of technologies that eventuate to connect information and expose it to humans. Presently, the SES is heterogeneous, fragmented and confined to semi-closed systems. A key issue hampering the emergence of an integrated SES is Service Discovery (SD). A SES will be dynamic with areas of structured and unstructured information within which service providers and ‘lay’ human consumers interact; until now the two are disjointed, e.g., SOA-enabled organisations, industries and domains are choreographed by domain experts or ‘hard-wired’ to smart device application markets and web applications. In a SES, services are accessible, comparable and exchangeable to human consumers closing the gap to the providers. This requires a new SD with which humans can discover services transparently and effectively without special knowledge or training. We propose two modes of discovery, directed search following an agenda and explorative search, which speculatively expands knowledge of an area of interest by means of categories. Inspired by conceptual space theory from cognitive science, we propose to implement the modes of discovery using concepts to map a lay consumer’s service need to terminologically sophisticated descriptions of services. To this end, we reframe SD as an information retrieval task on the information attached to services, such as, descriptions, reviews, documentation and web sites - the Service Information Shadow. The Semantic Space model transforms the shadow's unstructured semantic information into a geometric, concept-like representation. We introduce an improved and extended Semantic Space including categorization calling it the Semantic Service Discovery model. We evaluate our model with a highly relevant, service related corpus simulating a Service Information Shadow including manually constructed complex service agendas, as well as manual groupings of services. We compare our model against state-of-the-art information retrieval systems and clustering algorithms. By means of an extensive series of empirical evaluations, we establish optimal parameter settings for the semantic space model. The evaluations demonstrate the model’s effectiveness for SD in terms of retrieval precision over state-of-the-art information retrieval models (directed search) and the meaningful, automatic categorization of service related information, which shows potential to form the basis of a useful, cognitively motivated map of the SES for exploratory search.

Land fraud and inappropriate dealings in an electronic environment : An Australian and New Zealand perspective

The thesis presented in this paper is that the land fraud committed by Matthew Perrin in Queensland and inflicted upon Roger Mildenhall in Western Australia demonstrates the need for urgent procedural reform to the conveyancing process. Should this not occur, then calls to reform the substantive principles of the Torrens system will be heard throughout the jurisdictions that adopt title by registration, particularly in those places where immediate indefeasibility is still the norm. This paper closely examines the factual matrix behind both of these frauds, and asks what steps should have been taken to prevent them occurring. With 2012 bringing us Australian legislation embedding a national e-conveyancing system and a new Land Transfer Act for New Zealand we ask what legislative measures should be introduced to minimise the potential for such fraud. In undertaking this study, we reflect on whether the activities of Perrin and the criminals responsible for stealing Mildenhall's land would have succeeded under the present system for automated registration utilised in New Zealand.

Towards semantic search and inference in electronic medical records : an approach using concept-based information retrieval

Background This paper presents a novel approach to searching electronic medical records that is based on concept matching rather than keyword matching. Aim The concept-based approach is intended to overcome specific challenges we identified in searching medical records. Method Queries and documents were transformed from their term-based originals into medical concepts as defined by the SNOMED-CT ontology. Results Evaluation on a real-world collection of medical records showed our concept-based approach outperformed a keyword baseline by 25% in Mean Average Precision. Conclusion The concept-based approach provides a framework for further development of inference based search systems for dealing with medical data.

Frank-starling control of a left ventricular assist device

A physiological control system was developed for a rotary left ventricular assist device (LVAD) in which the target pump flow rate (LVADQ) was set as a function of left atrial pressure (LAP), mimicking the Frank-Starling mechanism. The control strategy was implemented using linear PID control and was evaluated in a pulsatile mock circulation loop using a prototyped centrifugal pump by varying pulmonary vascular resistance to alter venous return. The control strategy automatically varied pump speed (2460 to 1740 to 2700 RPM) in response to a decrease and subsequent increase in venous return. In contrast, a fixed-speed pump caused a simulated ventricular suction event during low venous return and higher ventricular volumes during high venous return. The preload sensitivity was increased from 0.011 L/min/mmHg in fixed speed mode to 0.47L/min/mmHg, a value similar to that of the native healthy heart. The sensitivity varied automatically to maintain the LAP and LVADQ within a predefined zone. This control strategy requires the implantation of a pressure sensor in the left atrium and a flow sensor around the outflow cannula of the LVAD. However, appropriate pressure sensor technology is not yet commercially available and so an alternative measure of preload such as pulsatility of pump signals should be investigated.

Thermally evaporated tungsten oxide (WO3) thin films for gas sensing applications

In this thesis, the author proposed and developed gas sensors made of nanostructured WO3 thin film by a thermal evaporation technique. This technique gives control over film thickness, grain size and purity. The device fabrication, nanostructured material synthesis, characterization and gas sensing performance have been undertaken. Three different types of nanostructured thin films, namely, pure WO3 thin films, iron-doped WO3 thin films by co-evaporation and Fe-implanted WO3 thin films have been synthesized. All the thin films have a film thickness of 300 nm. The physical, chemical and electronic properties of these films have been optimized by annealing heat treatment at 300ºC and 400ºC for 2 hours in air. Various analytical techniques were employed to characterize these films. Atomic Force Microscopy and Transmission Electron Microscopy revealed a very small grain size of the order 5-10 nm in as-deposited WO3 films, and annealing at 300ºC or 400ºC did not result in any significant change in grain size. X-ray diffraction (XRD) analysis revealed a highly amorphous structure of as-deposited films. Annealing at 300ºC for 2 hours in air did not improve crystallinity in these films. However, annealing at 400ºC for 2 hours in air significantly improved the crystallinity in pure and iron-doped WO3 thin films, whereas it only slightly improved the crystallinity of iron-implanted WO3 thin film as a result of implantation. Rutherford backscattered spectroscopy revealed an iron content of 0.5 at.% and 5.5 at.% in iron-doped and iron-implanted WO3 thin films, respectively. The RBS results have been confirmed using energy dispersive x-ray spectroscopy (EDX) during analysis of the films using transmission electron microscopy (TEM). X-ray photoelectron spectroscopy (XPS) revealed significant lowering of W 4f7/2 binding energy in all films annealed at 400ºC as compared with the as-deposited and 300ºC annealed films. Lowering of W 4f7/2 is due to increase in number of oxygen vacancies in the films and is considered highly beneficial for gas sensing. Raman analysis revealed that 400ºC annealed films except the iron-implanted film are highly crystalline with significant number of O-W-O bonds, which was consistent with the XRD results. Additionally, XRD, XPS and Raman analyses showed no evidence of secondary peaks corresponding to compounds of iron due to iron doping or implantation. This provided an understanding that iron was incorporated in the host WO3 matrix rather than as a separate dispersed compound or as catalyst on the surface. WO3 thin film based gas sensors are known to operate efficiently in the temperature range 200ºC-500 ºC. In the present study, by optimizing the physical, chemical and electronic properties through heat treatment and doping, an optimum response to H2, ethanol and CO has been achieved at a low operating temperature of 150ºC. Pure WO3 thin film annealed at 400ºC showed the highest sensitivity towards H2 at 150ºC due to its very small grain size and porosity, coupled with high number of oxygen vacancies, whereas Fe-doped WO3 film annealed at 400ºC showed the highest sensitivity to ethanol at an operating temperature of 150ºC due to its crystallinity, increased number of oxygen vacancies and higher degree of crystal distortions attributed to Fe addition. Pure WO3 films are known to be insensitive to CO, but iron-doped WO3 thin film annealed at 300ºC and 400ºC showed an optimum response to CO at an operating temperature of 150ºC. This result is attributed to lattice distortions produced in WO3 host matrix as a result of iron incorporation as substitutional impurity. However, iron-implanted WO3 thin films did not show any promising response towards the tested gases as the film structure has been damaged due to implantation, and annealing at 300ºC or 400ºC was not sufficient to induce crystallinity in these films. This study has demonstrated enhanced sensing properties of WO3 thin film sensors towards CO at lower operating temperature, which was achieved by optimizing the physical, chemical and electronic properties of the WO3 film through Fe doping and annealing. This study can be further extended to systematically investigate the effects of different Fe concentrations (0.5 at.% to 10 at.%) on the sensing performance of WO3 thin film gas sensors towards CO.

Videogame control device impact on the play experience

New types of control devices for videogames have emerged and expanded the demographics of the game playing public, yet little is known about which populations of gamers prefer which style of interaction and why. This paper presents data from a study that seeks to clarify the influence the control interface has on the play experience. Three commercial control devices were categorised using an existing typology, according to how the interface maps physical control inputs with the virtual gameplay actions. The devices were then used in a within-groups experimental design aimed at measuring differences in play experience across 64 participants. Descriptive analysis is undertaken on the performance, play experience and preference results for each device. Potential explanations for these results are discussed, as well as the direction of future work.

Personalised electronic messages to improve sun protection in young adults

The incidence of all skin cancers, including melanoma, continues to rise. It is well known that ultraviolet (UV) radiation is the main environmental risk factor for skin cancer, and excessive exposure at a young age increases the risk of developing skin cancer. The aim of this study was to determine the acceptability and feasibility of delivering sun protection messages via electronic media such as short message services (SMS) to people 18-40 years, and explore factors associated with their acceptability. Overall, 80% of participants agreed that they would like to receive some form of sun protection advice; of these, 20% prefer to receive it via SMS and 42% via email. Willingness to receive electronic messages about the UV index was associated with being unsure about whether a suntanned person would look healthy and greater use of sun protection in the past. Careful attention to message framing and timing of message delivery and focus on short-term effects of sun exposure such as sunburn and skin ageing should increase the acceptability of such messages to young people. We conclude that sun protection messages delivered to young adults via electronic media appear feasible and acceptable.

Efficacy of oral or intrauterine device-delivered progestin in patients with complex endometrial hyperplasia with atypia or early endometrial adenocarcinoma : a meta-analysis and systematic review of the literature

Objectives: To investigate the efficacy of progestin treatment to achieve pathological complete response (pCR) in patients with complex atypical endometrial hyperplasia (CAH) or early endometrial adenocarcinoma (EC). Methods: A systematic search identified 3245 potentially relevant citations. Studies containing less than ten eligible CAH or EC patients in either oral or intrauterine treatment arm were excluded. Only information from patients receiving six or more months of treatment and not receiving other treatments was included. Weighted proportions of patients achieving pCR were calculated using R software. Results: Twelve studies met the selection criteria. Eleven studies reported treatment of patients with oral (219 patients, 117 with CAH, 102 with grade 1 Stage I EC) and one reported treatment of patients with intrauterine progestin (11 patients with grade 1 Stage IEC). Overall, 74% (95% confidence interval [CI] 65-81%) of patients with CAH and 72% (95% CI 62-80%) of patients with grade 1 Stage I EC achieved a pCR to oral progestin. Disease progression while on oral treatment was reported for 6/219 (2.7%), and relapse after initial complete response for 32/159 (20.1%) patients. The weighted mean pCR rate of patients with grade 1 Stage I EC treated with intrauterine progestin from one prospective pilot study and an unpublished retrospective case series from the Queensland Centre of Gynaecologic Oncology (QCGC) was 68% (95% CI 45- 86%). Conclusions: There is a lack of high quality evidence for the efficacy of progestin in CAH or EC. The available evidence however suggests that treatment with oral or intrauterine progestin is similarly effective. The risk of progression during treatment is small but longer follow-up is required. Evidence from prospective controlled clinical trials is warranted to establish how the efficacy of progestin for the treatment of CAH and EC can be improved further.

Intravascular device-related research : future priority areas for cancer nursing

The majority of cancer nurses have to manage intravascular devices (IVDs) on a daily basis, thus placing nurses in the strongest position to generate and use best available evidence to inform this area of practice and to ensure that patients are receiving the best care available. Our literature clearly reflects that cancer nurses are concerned about complications associated with IVDs (eg, extravasation,1 IVD-related bloodstream infection [IVD-BSI],2,3 and thrombosis4). Although enormous attention is given to this area, a number of nursing practices are not sufficiently based on empirical evidence.5,6 Nurses need to set goals and priorities for future research and investments. Priority areas for future research are suggested here for your consideration.

National electronic conveyancing : outline of national law and rules

This article will outline the impact of the Electronic Conveyancing National Law (ECNL) and the draft Model Participation Rules (MPR) on conveyancing practice and the obligations of lawyers and conveyancers.