New dimeric supramolecular structure of mixed (phthalocyaninato)(porphyrinato)-europium(III) sandwiches : preparation and spectroscopic characteristics

The mixed double-decker Eu\[Pc(15C5)4](TPP) (1) was obtained by base-catalysed tetramerisation of 4,5-dicyanobenzo-15-crown-5 using the half-sandwich complex Eu(TPP)(acac) (acac = acetylacetonate), generated in situ, as the template. For comparative studies, the mixed triple-decker complexes Eu2\[Pc(15C5)4](TPP)2 (2) and Eu2\[Pc(15C5)4]2(TPP) (3) were also synthesised by the raise-by-one-story method. These mixed ring sandwich complexes were characterised by various spectroscopic methods. Up to four one-electron oxidations and two one-electron reductions were revealed by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). As shown by electronic absorption and infrared spectroscopy, supramolecular dimers (SM1 and SM3) were formed from the corresponding double-decker 1 and triple-decker 3 in the presence of potassium ions in MeOH/CHCl3.

Elevated concentration of TNF-a induces trophoblast differentiation in mouse blastocyst outgrowths

Elevated expression of tumour necrosis factora (TNF-a) is associated with adverse pregnancy outcome. This study has examined the expression of TNF-a and its receptors (TNF-Rs) by mouse blastocysts and blastocyst outgrowths from day 4 to 9.5 of pregnancy and investigated the effects of elevated TNF-a on the inner cell mass (ICM) and trophoblast cells of blastocyst outgrowths. RTPCR demonstrated TNF-a mRNA expression from day 7.5 to 9.5, TNF-R1 from day 6.5 to 9.5 and TNF-R2 from day 5.5 to 7.5 of pregnancy, and in situ hybridisation revealed the trophoblast giant cells (TGCs) of the early placenta as the site of TNF-a expression. Day 4 blastocysts were cultured in a physiologically high concentration of TNF-a (100 ng/ml) for 72 h to the outgrowth stage and then compared to blastocysts cultured in media alone. TNF-a-treated blastocyst outgrowths exhibited a significant reduction in ICM cells (mean € SD 23.90€10.42 vs 9.37€7.45, t-test, P<0.0001) with no significant change in the numbers of trophoblast cells (19.97€8.14 vs 21.73€7.79, t-test, P=0.39). Within the trophoblast cell population, the TNF-a-treated outgrowths exhibited a significant increase in multinucleated cells (14.10€5.53 vs 6.37€5.80, t-test, P<0.0001) and a corresponding significant decrease in mononucleated cells (5.87€3.60 vs 15.37€5.87, t-test, P<0.0001). In summary, this study describes the expression of TNF-a and its receptors during the peri-implantation period in the mouse. It also reports that elevated TNF-a restricts ICM proliferation in the blastocyst and changes the ratio of mononucleated to multinucleated trophoblast cells. These findings suggest a mechanism by which increased

Lady Nugent and Tom Cringle on the veranda : early nineteenth century observations on a Caribbean architectural feature

This study of the veranda as seen through the eyes of Lady Maria Nugent and Michael Scott, alias Tom Cringle, clearly demonstrates the important role that the piazza, as it was then more commonly known, played in the life of early nineteenth century Caribbean colonial society. The popularity of the veranda throughout the region, in places influenced by different European as well as African cultures, and among all classes of people, suggests that the appeal of this typical feature was based on something more than architectural fashion. A place of relative comfort in hot weather, the veranda is also a space at the interface of indoors and outdoors which allows for a wide variety of uses, for solitary or small or large group activities, many of which were noted by Nugent and Scott. Quintessentially, the veranda is a place in which to relax and take pleasure, not least of which is the enjoyment of the prospect, be it a panoramic view, a peaceful garden or a lively street scene. Despite the great changes in the nature of society, in the Caribbean and in many other parts of the world, the veranda and related structures such as the balcony continue to play at least as important a role in daily life as they did two centuries ago. The veranda of today’s Californian or Australian bungalow, and the balcony of the apartment block in the residential area of the modern city are among the contemporary equivalents of the lower and upper piazzas of Lady Nugent’s and Tom Cringle’s day.

Tuning the valence of the cerium center in (Na)phthalocyaninato and porphyrinato cerium double-deckers by changing the nature of the tetrapyrrole ligands

A series of 7 cerium double-decker complexes with various tetrapyrrole ligands including porphyrinates, phthalocyaninates, and 2,3-naphthalocyaninates have been prepared by previously described methodologies and characterized with elemental analysis and a range of spectroscopic methods. The molecular structures of two heteroleptic \[(na)phthalocyaninato](porphyrinato) complexes have also been determined by X-ray diffraction analysis which exhibit a slightly distorted square antiprismatic geometry with two domed ligands. Having a range of tetrapyrrole ligands with very different electronic properties, these compounds have been systematically investigated for the effects of ligands on the valence of the cerium center. On the basis of the spectroscopic (UV−vis, near-IR, IR, and Raman), electrochemical, and structural data of these compounds and compared with those of the other rare earth(III) counterparts reported earlier, it has been found that the cerium center adopts an intermediate valence in these complexes. It assumes a virtually trivalent state in cerium bis(tetra-tert-butylnaphthalocyaninate) as a result of the two electron rich naphthalocyaninato ligands, which facilitate the delocalization of electron from the ligands to the metal center. For the rest of the cerium double-deckers, the cerium center is predominantly tetravalent. The valences (3.59−3.68) have been quantified according to their LIII-edge X-ray absorption near-edge structure (XANES) profiles.

A maintenance-data-model of enterprise resource planning

Two distinct maintenance-data-models are studied: a government Enterprise Resource Planning (ERP) maintenance-data-model, and the Software Engineering Industries (SEI) maintenance-data-model. The objective is to: (i) determine whether the SEI maintenance-data-model is sufficient in the context of ERP (by comparing with an ERP case), (ii) identify whether the ERP maintenance-data-model in this study has adequately captured the essential and common maintenance attributes (by comparing with the SEI), and (iii) proposed a new ERP maintenance-data-model as necessary. Our findings suggest that: (i) there are variations to the SEI model in an ERP-context, and (ii) there are rooms for improvements in our ERP case’s maintenance-data-model. Thus, a new ERP maintenance-data-model capturing the fundamental ERP maintenance attributes is proposed. This model is imperative for: (i) enhancing the reporting and visibility of maintenance activities, (ii) monitoring of the maintenance problems, resolutions and performance, and (iii) helping maintenance manager to better manage maintenance activities and make well-informed maintenance decisions.

Technological barriers to learning : designing hybrid pedagogy to minimise cognitive load and maximise understanding

Information and Communication Technologies (ICTs) provide great promise for the future of education. In the Asia-Pacific region, many nations have started working towards the comprehensive development of infrastructure to enable the development of strong networked educational systems. In Queensland there have been significant initiatives in the past decade to support the integration of technology in classrooms and to set the conditions for the enhancement of teaching and learning with technology. One of the great challenges is to develop our classrooms to make the most of these technologies for the benefit of student learning. Recent research and theory into cognitive load, suggests that complex information environments may well impose a barrier on student learning. Further, it suggests that teachers have the capacity to mitigate against cognitive load through the way they prepare and support students engaging with complex information environments. This chapter compares student learning at different levels of cognitive load to show that learning is enhanced when integrating pedagogies are employed to mitigate against high-load information environments. This suggests that a mature policy framework for ICTs in education needs to consider carefully the development of professional capacities to effectively design and integrate technologies for learning.

Maintaining ERP packaged software : a revelatory case study

For many organizations, maintaining and upgrading enterprise resource planning (ERP) systems (large packaged application software) is often far more costly than the initial implementation. Systematic planning and knowledge of the fundamental maintenance processes and maintenance-related management data are required in order to effectively and efficiently administer maintenance activities. This paper reports a revelatory case study of Government Services Provider (GSP), a high-performing ERP service provider to government agencies in Australia. GSP ERP maintenance-process and maintenance-data standards are compared with the IEEE/EIA 12207 software engineering standard for custom software, also drawing upon published research, to identify how practices in the ERP context diverge from the IEEE standard. While the results show that many best practices reflected in the IEEE standard have broad relevance to software generally, divergent practices in the ERP context necessitate a shift in management focus, additional responsibilities, and different maintenance decision criteria. Study findings may provide useful guidance to practitioners, as well as input to the IEEE and other related standards.