A concise approach to the polycyclic scaffold of frondosin D

Frondosins A−E, 1−5 (Figure 1), are a family of related marine sesquiterpenoids first isolated in their dextro-rotatory form from the sponge Dysidea frondosa.(1a) Additionally, levo-rotatory frondosins A and D were isolated from an unidentified Eurospongia species.(1b) Frondosins A−E are compounds of interest due to their promising interleukin-8 (IL-8) affinity and protein kinase C inhibition.(1a) IL-8 antagonists are of particular interest in view of their antiinflammatory,(2a) anti-HIV,(1b, 2b) and antitumor(2c-2f) properties. To date, frondosins A, B, and C have been synthesized.(3) Notwithstanding these successes, the frondosins have proved quite a formidable synthetic challenge, and as of yet, there has been no synthesis of frondosin D or E. In this report, we describe our approaches to the molecular scaffold of frondosins D. This work has culminated in a very effective means of producing the trimethylbicyclo[5.4.0]undecane ring system common to all frondosins (shown in bold, Figure 1).

Xanthones from fungi, lichens, and bacteria : the natural products and their synthesis

Many fungi, lichens, and bacteria produce xanthones (derivatives of 9H-xanthen-9-one, “xanthone” from the Greek “xanthos”, for “yellow”) as secondary metabolites. Xanthones are typically polysubstituted and occur as either fully aromatized, dihydro-, tetrahydro-, or, more rarely, hexahydro-derivatives. This family of compounds appeals to medicinal chemists because of their pronounced biological activity within a notably broad spectrum of disease states, a result of their interaction with a correspondingly diverse range of target biomolecules. This has led to the description of xanthones as “privileged structures”.(1) Historically, the total synthesis of the natural products has mostly been limited to fully aromatized targets. Syntheses of the more challenging partially saturated xanthones have less frequently been reported, although the development in recent times of novel and reliable methods for the construction of the (polysubstituted) unsaturated xanthone core holds promise for future endeavors. In particular, the fascinating structural and biological properties of xanthone dimers and heterodimers may excite the synthetic or natural product chemist.

ortho-Bromo(propa-1,2-dien-1-yl)arenes : substrates for domino reactions

o-Bromo(propa-1,2-dien-1-yl)arenes exhibit novel and orthogonal reactivity under Pd catalysis in the presence of secondary amines to form enamines (concerted Pd insertion, intramolecular carbopalladation, and terminative Buchwald–Hartwig coupling) and of amides to form indoles (addition, Buchwald–Hartwig cyclization, and loss of the acetyl group). The substrates for these reactions can be accessed in a reliable and highly selective two-step process from 2-bromoaryl bromides.

IODP Expedition 339 in the Gulf of Cadiz and off West Iberia : decoding the environmental significance of the Mediterranean outflow water and its global influence

IODP Expedition 339 drilled five sites in the Gulf of Cadiz and two off the west Iberian margin (November 2011 to January 2012), and recovered 5.5 km of sediment cores with an average recovery of 86.4%. The Gulf of Cadiz was targeted for drilling as a key location for the investigation of Mediterranean outflow water (MOW) through the Gibraltar Gateway and its influence on global circulation and climate. It is also a prime area for understanding the effects of tectonic activity on evolution of the Gibraltar Gateway and on margin sedimentation. We penetrated into the Miocene at two different sites and established a strong signal of MOW in the sedimentary record of the Gulf of Cadiz, following the opening of the Gibraltar Gateway. Preliminary results show the initiation of contourite deposition at 4.2–4.5 Ma, although subsequent research will establish whether this dates the onset of MOW. The Pliocene succession, penetrated at four sites, shows low bottom current activity linked with a weak MOW. Significant widespread unconformities, present in all sites but with hiatuses of variable duration, are interpreted as a signal of intensified MOW, coupled with flow confinement. The Quaternary succession shows a much more pronounced phase of contourite drift development, with two periods of MOW intensification separated by a widespread unconformity. Following this, the final phase of drift evolution established the contourite depositional system (CDS) architecture we see today. There is a significant climate control on this evolution of MOW and bottom-current activity. However, from the closure of the Atlantic–Mediterranean gateways in Spain and Morocco just over 6 Ma and the opening of the Gibraltar Gateway at 5.3 Ma, there has been an even stronger tectonic control on margin development, downslope sediment transport and contourite drift evolution. The Gulf of Cadiz is the world's premier contourite laboratory and thus presents an ideal testing ground for the contourite paradigm. Further study of these contourites will allow us to resolve outstanding issues related to depositional processes, drift budgets, and recognition of fossil contourites in the ancient record on shore. The expedition also verified an enormous quantity and extensive distribution of contourite sands that are clean and well sorted. These represent a relatively untapped and important exploration target for potential oil and gas reservoirs.

The Australian Nonprofit Sector Legal and Accounting Almanac 2013

INTRODUCTION CASES For a number of years, Professor Myles McGregor-Lowndes, Frances Hannah and Anne Overell have compiled one to two page summaries of cases involving nonprofit organisations and published them on The Australian Centre for Philanthropy and Nonprofit Studies, Developing Your Organisation (DYO) website.1 You can be alerted of new case summaries as they are posted to the DYO website by subscribing to the ACPNS RSS feed or the ACPNS twitter service.2 There were some very significant cases during 2013, such as Commissioner of Taxation v Cancer & Bowel Research Association (see case notes 2.8.2 and 2.8.11), The Hunger Project case which is under appeal, but could change the face of PBI jurisprudence (see case note 2.8.7) while Home Health Pty Ltd retained the PBI status quo but might have been different if appealed (see case note 2.8.8). For sheer interest there is nothing better in my 30 odd years of reading tax and charity judgements than case involving The Study and Prevention of Psychological Diseases Foundation Incorporated (see case note 2.1.1). It even rivals some of the more bizarre cases from the US jurisdiction of which St Joseph Abbey v Castille (case note 2.10.9) is certainly ‘dead centre’. A set of cases which stand out for attention are those involving New Zealand’s Christchurch Cathedral which anyone with responsibility for heritage-listed buildings should study carefully, for implications in relation to their own circumstances. A number of cases summarised in this Almanac are working their way through the appeals process and care should be taken with their application. In addition, some of the cases are from jurisdictions outside Australia, and readers should exercise caution when considering the implications of these cases for Australian law. LEGISLATION The Almanac includes a review of major statutory amendments during 2013, which are relevant to the nonprofit sector in all Australian jurisdictions. Special thanks must go to Nathan MacDonald and the JusticeConnect team for providing legislative updates for Victoria. SPECIAL ISSUES DURING 2013 A number of legal practitioners have contributed articles on significant legal issues facing nonprofit organisations: charitable trusts giving to government entities (Alice Macdougall); workplace bullying (Tim Longwill); and privacy (James Tan and Nina Brewer). WORLD ROUND-UP Major developments from the UK and Ireland (Kerry O’Halloran), Canada (Peter Broder), New Zealand (Michael Gousmett and Susan Barker) and Jamaica (Frances Hannah) are all summarised in a review of a significant part of the common law charity jurisdictions. WHAT DOES 2014 HOLD The final section moves from looking in the rear view mirror to peering out the front windscreen to discern the reform agenda. The view from the windscreen in 2013 was of considerable reform traffic at the Commonwealth level jostling for a place in the parliamentary agenda. This year is quite different with a smaller number of vehicles ahead, but the potential for significant impact.

Safety management in repair, maintenance, minor alteration, and addition works : knowledge management perspective

Safety of repair, maintenance, alteration, and addition (RMAA) works have long been neglected because RMAAworks are often minute and only last for a short period of time. With rising importance of the RMAA sector in many developed societies, safety of RMAA works has begun to draw attention. Many RMAA contracting companies are small- and medium-sized enterprises (SMEs) that do not have comprehensive safety management systems. Existing safety legislation and regulations for new construction sites are not fully applicable to RMAAworks. Instead of relying on explicit and well-established safety systems, tacit safety knowledge plays an extremely important role in RMAA projects. To improve safety of RMAAworks, safety knowledge should be better managed. However, safety knowledge is difficult to capture in RMAA works. This study aims to examine safety management practices of RMAA contracting companies to see how safety knowledge of RMAA projects is managed. Findings show that RMAA contracting companies undertaking large-scale RMAA projects have more initiatives of safety management. Safety management of small-scale RMAA works relies heavily on the motivation of site supervisors and self-regulation of workers. Better tacit knowledge management improves safety performance. To enhance safety capability of RMAA contracting companies, a knowledge sharing culture should be cultivated. The government should provide assistance to SMEs to implement proper safety management practices in small-sized projects. Potentials of applying computer software technology in RMAA projects to capture, store, and retrieve safety information should be explored. Employees should be motivated to share safety knowledge by giving proper recognition to those who are willing to share.

Are lifecycle funds appropriate as default options in participant-directed retirement plans?

The appropriateness of default investment options in participant-directed retirement plans like 401(k) has been in sharp focus given that most participants fail to nominate an investment option to direct their contributions. In United States (US), prior to the Pension Protection Act (PPA) of 2006, plan fiduciaries often selected a money market fund as the default option. Whilst this ‘low risk and low return’ investment option was considered to be a ‘safe’ choice by many fiduciaries who were fearful of litigation risk, it was heavily criticized for resulting in inadequate wealth at retirement, particularly when retirees were living much longer and facing inflation risk (see, for example, Viceira, 2008; Skinner, 2009)...

Factor Five : Transforming the Global Economy through 80% Improvements in Resource Productivity

The 21st century will see monumental change. Either the human race will use its knowledge and skills and change the way it interacts with the environment, or the environment will change the way it interacts with its inhabitants. In the first case, the focus of this book, we would see our sophisticated understanding in areas such as physics, chemistry, engineering, biology, planning, commerce, business and governance accumulated over the last 1,000 years brought to bear on the challenge of dramatically reducing our pressure on the environment. The second case however is the opposite scenario, involving the decline of the planet’s ecosystems until they reach thresholds where recovery is not possible, and following which we have no idea what happens. For instance, if we fail to respond to Sir Nicolas Stern’s call to meet appropriate stabilisation trajectories for greenhouse gas emissions, and we allow the average temperature of our planets surface to increase by 4-6 degrees Celsius, we will see staggering changes to our environment, including rapidly rising sea level, withering crops, diminishing water reserves, drought, cyclones, floods… allowing this to happen will be the failure of our species, and those that survive will have a deadly legacy. In this update to the 1997 International Best Seller, Factor Four, Ernst von Weizsäcker again leads a team to present a compelling case for sector wide advances that can deliver significant resource productivity improvements over the coming century. The purpose of this book is to inspire hope and to then inform meaningful action in the coming decades to respond to the greatest challenge our species has ever faced – that of living in harmony with our planet and its other inhabitants.

“Creep-out” versus “gross-out” : horror movies at the Australian Box Office

Australia is a difficult market for horror movies. Particularly in recent years, Australia has been regarded as a graveyard for many horror films released theatrically. This is not to say that Australians have not enjoyed the occasional scary movie on the big screen. But what types of horror films have been popular with Australian audiences at the box-office remains poorly understood. Horror films revolve around monsters, the fear of death and the transgression of boundaries, and they aim to scare audiences through ‘gross-out’ or ‘creep-out’ factors (some combine both). The former refers to shocking and graphic portrayals of gore and violence – as seen in the sadistic torture of backpackers in Hostel (Eli Roth, 2005), which depicts limbs being hacked off and eyes being cut from nerve endings. The latter refers to the crafting of fear through mood and suspense without explicit bloodshed, achieved brilliantly in The Sixth Sense’s (M Night Shyamalan, 1999) chilling encounters with ‘dead people’. In creep-out films, it is often what viewers don’t see that is most disturbing. Using an analysis of the top fifty films each year at the Australian box office from 1992 to 2012, this article identifies the most successful horror movies over this period to ascertain what types of horror movies – with reference to creep-out and gross-out factors – have been most popular with domestic audiences.

Free-riding, cooperation, and 'peaceful revolutions' in copyright

Modern copyright law is based on the inescapable assumption that users, given the choice, will free-ride rather than pay for access. In fact, many consumers of cultural works – music, books, films, games, and other works – fundamentally want to support their production. It turns out that humans are motivated to support cultural production not only by extrinsic incentives, but also by social norms of fairness and reciprocity. This article explains how producers across the creative industries have used this insight to develop increasingly sophisticated business models that rely on voluntary payments (including pay-what-you-want schemes) to fund their costs of production. The recognition that users are not always free-riders suggests that current policy approaches to copyright are fundamentally flawed. Because social norms are so important in consumer motivations, the perceived unfairness of the current copyright system undermines the willingness of people to pay for access to cultural goods. While recent copyright reform debate has focused on creating stronger deterrence through enforcement, increasing the perceived fairness and legitimacy of copyright law is likely to be much more effective. The fact that users will sometimes willingly support cultural production also challenges the economic raison d'être of copyright law. This article demonstrates how 'peaceful revolutions' are flipping conventional copyright models and encouraging free-riding through combining incentives and prosocial norms. Because they provide a means to support production without limiting the dissemination of knowledge and culture, there is good reason to believe that these commons-based systems of cultural production can be more efficient, more fair, and more conducive to human flourishing than conventional copyright systems. This article explains what we know about free-riding so far and what work remains to be done to understand the viability and importance of cooperative systems in funding cultural production.

Innovations in dietetic training in foodservice management : can early exposure to practice enhance final year competency development?

Student engagement in the delivery of theoretical course materials is a current challenge in the tertiary sector including for dietetic training. In 2011 with the creation of a new nutritionist position for Queensland Meals on Wheels (QMOW), a service learning approach to support this organisation was used with third year dietetic students undertaking two days of structured activities at various QMOW sites in South East Queensland, aligned with coursework in Foodservice Management (FSM). This cohort of students was then followed in their final year post successful completion of five weeks professional practice in FSM to see if this experience supported readiness for placement and competency development. Evaluation was undertaken of eligible students (n = 50) via paper based survey (response rate 94%) with all participating in targeted focus groups. Findings showed that students acknowledged the QMOW experience (on reflection 14 months later) providing opportunity for participation and/or observation in 5 of 12 FSM areas taught in third year, including food safety, meal production, assembly, delivery and dishwashing. Over half the students identified good exposure to FSM competency areas during the QMOW experience, with 83% satisfied with their competency exposure and subsequent practice during final year placements. A consistent theme emerged from focus groups supporting inclusion of practical opportunities with the theoretical component of the FSM subject to highlight relevance to learning. These findings highlight the importance of such teaching initiatives to met student learning preferences, linking theory with practice and supporting competency development in the final year of training programs.

Integrated approach for diagnostics and prognostics of HP LNG pump based on health state probability estimation

Effective machine fault prognostic technologies can lead to elimination of unscheduled downtime and increase machine useful life and consequently lead to reduction of maintenance costs as well as prevention of human casualties in real engineering asset management. This paper presents a technique for accurate assessment of the remnant life of machines based on health state probability estimation technique and historical failure knowledge embedded in the closed loop diagnostic and prognostic system. To estimate a discrete machine degradation state which can represent the complex nature of machine degradation effectively, the proposed prognostic model employed a classification algorithm which can use a number of damage sensitive features compared to conventional time series analysis techniques for accurate long-term prediction. To validate the feasibility of the proposed model, the five different level data of typical four faults from High Pressure Liquefied Natural Gas (HP-LNG) pumps were used for the comparison of intelligent diagnostic test using five different classification algorithms. In addition, two sets of impeller-rub data were analysed and employed to predict the remnant life of pump based on estimation of health state probability using the Support Vector Machine (SVM) classifier. The results obtained were very encouraging and showed that the proposed prognostics system has the potential to be used as an estimation tool for machine remnant life prediction in real life industrial applications.

Fault diagnosis of low speed bearing based on acoustic emission signal and multi-class relevance vector machine

This study presents an acoustic emission (AE) based fault diagnosis for low speed bearing using multi-class relevance vector machine (RVM). A low speed test rig was developed to simulate the various defects with shaft speeds as low as 10 rpm under several loading conditions. The data was acquired using anAEsensor with the test bearing operating at a constant loading (5 kN) andwith a speed range from20 to 80 rpm. This study is aimed at finding a reliable method/tool for low speed machines fault diagnosis based on AE signal. In the present study, component analysis was performed to extract the bearing feature and to reduce the dimensionality of original data feature. The result shows that multi-class RVM offers a promising approach for fault diagnosis of low speed machines.

Output feedback optimal control with contraints

In Chapters 1 through 9 of the book (with the exception of a brief discussion on observers and integral action in Section 5.5 of Chapter 5) we considered constrained optimal control problems for systems without uncertainty, that is, with no unmodelled dynamics or disturbances, and where the full state was available for measurement. More realistically, however, it is necessary to consider control problems for systems with uncertainty. This chapter addresses some of the issues that arise in this situation. As in Chapter 9, we adopt a stochastic description of uncertainty, which associates probability distributions to the uncertain elements, that is, disturbances and initial conditions. (See Section 12.6 for references to alternative approaches to model uncertainty.) When incomplete state information exists, a popular observer-based control strategy in the presence of stochastic disturbances is to use the certainty equivalence [CE] principle, introduced in Section 5.5 of Chapter 5 for deterministic systems. In the stochastic framework, CE consists of estimating the state and then using these estimates as if they were the true state in the control law that results if the problem were formulated as a deterministic problem (that is, without uncertainty). This strategy is motivated by the unconstrained problem with a quadratic objective function, for which CE is indeed the optimal solution (˚Astr¨om 1970, Bertsekas 1976). One of the aims of this chapter is to explore the issues that arise from the use of CE in RHC in the presence of constraints. We then turn to the obvious question about the optimality of the CE principle. We show that CE is, indeed, not optimal in general. We also analyse the possibility of obtaining truly optimal solutions for single input linear systems with input constraints and uncertainty related to output feedback and stochastic disturbances.We first find the optimal solution for the case of horizon N = 1, and then we indicate the complications that arise in the case of horizon N = 2. Our conclusion is that, for the case of linear constrained systems, the extra effort involved in the optimal feedback policy is probably not justified in practice. Indeed, we show by example that CE can give near optimal performance. We thus advocate this approach in real applications.

Disclosures of social value creation : a case study of three global social enterprises

This study seeks to fill in gap in the existing literature by looking at how and whether disclosure of social value creation becomes a part of legitimation strategies of social enterprises. By using legitimacy reasoning, this study informs that three global social organizations, Grameen Bank, Charity Water, and the Bill and Melinda Gates Foundation provide evidence of the use of disclosures of social value creation in order to conform with the expectations of the broader community—the community that wants to see poverty and injustice free world.