Studies in terpenoids. Part XXX. Synthesis of pterosin E, a sesquiter-penoid from bracken

Pterosin E (2,5,7-trimethyl-1-oxoindan-6-ylacetic acid)(Ia), a naturally occurring sesquiterpenoid has been synthesized starting from -bromomesitylene (IIIa). Alkylation of diethyl methylmalonate with (IIIa) gave the diester (IIIb) which was converted into the cyanomethyl diester (IVb). Hydrolysis of (IVb) to the dicarboxylic acid (V) followed by its cyclodehydration gave pterosin E.

Structural studies of analgesics and their interactions. Part 4. Crystal structures of phenylbutazone and a 2 : 1 complex between phenylbutazone and piperazine

The X-ray crystal structures of 4-butyl-1,2-diphenylpyrazolidine-3,5-dione (phenylbutazone)(I). and its 2 : 1 complex (II) with piperazine have been determined by direct methods and the structures refined to R 0.096 (2 300 observed reflections measured by diffractometer) and 0.074 (2 494 observed reflections visuallyestimated). Crystals are monoclinic, space group P21/c; for (I)a= 21.695(4), b= 5.823(2), c= 27.881(4)Å, = 108.06 (10)°, Z= 8, and for (II)a= 8.048(4), b= 15.081(4), c= 15.583(7)Å, = 95.9(3)°, Z= 2. The two crystallographically independant molecules in the structure of (I) are similar except for the conformation of the butyl group, which is disordered in one of the molecules. In the pyrazolidinedione group, the two C–C bonds are single and the two C–O bonds double. The two nitrogen atoms in the five-membered ring are pyramidal with the attached phenyl groups lying on the opposite sides of the mean plane of the ring. The phenylbutazone molecule in (II) exists as a negative ion owing to deprotonation of C-4. C-4 is therefore trigonal and the orientation of the Bu group with respect to the pyrazolidinedione group is considerably different from that in (I); there is also considerable electron delocalization along the C–O and C–C bonds. These changes in geometry and electronic structure may relate to biological activity. The doubly charged cationic piperazine molecule exists in the chair form with the nitrogen atoms at the apices. The crystal structure of (II) is stabilized by ionic interactions and N–H O hydrogen bonds.

DMT of Multi-hop Cooperative Networks-Part II: Layered and Multi-Antenna Networks

We consider single-source, single-sink (ss-ss) multi-hop relay networks, with slow-fading Rayleigh links. This two part paper aims at giving explicit protocols and codes to achieve the optimal diversity-multiplexing tradeoff (DMT) of two classes of multi-hop networks: K-parallel-path (KPP) networks and Layered networks. While single-antenna KPP networks were the focus of the first part, we consider layered and multi-antenna networks in this second part. We prove that a linear DMT between the maximum diversity d(max). and the maximum multiplexing gain of 1 is achievable for single-antenna fully-connected layered networks under the half-duplex constraint. This is shown to be equal to the optimal DMT if the number of relaying layers is less than 4. For the multiple-antenna case, we provide an achievable DMT, which is significantly better than known lower bounds for half duplex networks. Along the way, we compute the DMT of parallel MIMO channels in terms of the DMT of the component channel. For arbitrary ss-ss single-antenna directed acyclic networks with full-duplex relays, we prove that a linear tradeoff between maximum diversity and maximum multiplexing gain is achievable using an amplify-and-forward (AF) protocol. Explicit short-block-length codes are provided for all the proposed protocols. Two key implications of the results in the two-part paper are that the half-duplex constraint does not necessarily entail rate loss by a factor of two as previously believed and that simple AN protocols are often sufficient to attain the best possible DMT.

DMT of Multi-hop Cooperative Networks-Part I: K-Parallel-Path Networks

We consider single-source, single-sink multi-hop relay networks, with slow-fading Rayleigh fading links and single-antenna relay nodes operating under the half-duplex constraint. While two hop relay networks have been studied in great detail in terms of the diversity-multiplexing tradeoff (DMT), few results are available for more general networks. In this two-part paper, we identify two families of networks that are multi-hop generalizations of the two hop network: K-Parallel-Path (KPP) networks and Layered networks. In the first part, we initially consider KPP networks, which can be viewed as the union of K node-disjoint parallel paths, each of length > 1. The results are then generalized to KPP(I) networks, which permit interference between paths and to KPP(D) networks, which possess a direct link from source to sink. We characterize the optimal DMT of KPP(D) networks with K >= 4, and KPP(I) networks with K >= 3. Along the way, we derive lower bounds for the DMT of triangular channel matrices, which are useful in DMT computation of various protocols. As a special case, the DMT of two-hop relay network without direct link is obtained. Two key implications of the results in the two-part paper are that the half-duplex constraint does not necessarily entail rate loss by a factor of two, as previously believed and that, simple AF protocols are often sufficient to attain the best possible DMT.

‘Enough is enough’: Songs and messages about alcohol in remote Central Australia

This article examines some of the ways in which Australia’s First Peoples have responded to serious community health concerns about alcohol through the medium of popular music. The writing, performing and recording of popular songs about alcohol provide an important example of community-led responses to health issues, and the effectiveness of music in communicating stories and messages about alcohol has been recognised through various government-funded recording projects. This article describes some of these issues in remote Australian Aboriginal communities, exploring a number of complexities that arise through arts-based ‘instrumentalist’ approaches to social and health issues. It draws on the author’s own experience and collaborative work with Aboriginal musicians in Tennant Creek, a remote town in Australia’s Northern Territory.

The paradigm of relevance: Is it time to kill the sacred cow?

Prior to embarking on further study into the subject of relevance it is essential to consider why the concept of relevance has remained inconclusive, despite extensive research and its centrality to the discipline of information science. The approach taken in this paper is to reconstruct the science of information retrieval from first principles including the problem statement, role, scope and objective. This framework for document selection is put forward as a straw man for comparison with the historical relevance models. The paper examines five influential relevance models over the past 50 years. Each is examined with respect to its treatment of relevance and compared with the first principles model to identify contributions and deficiencies. The major conclusion drawn is that relevance is a significantly overloaded concept which is both confusing and detrimental to the science.

Learning to write: Analysing writing samples as part of considering how children become writers

This chapter draws on a large data set of children's work samples collected as part of a five-year school reform project in a community of high poverty. One component of the data set from this project is a corpus of more than 2000 writing samples collected from students across eight grade levels (Prep to year 7) annually, across four years of the project (2009-2013). This paper utilises a selection of these texts to consider insights available to teachers and schools through a simple process of collecting and assessing writing samples produced by children over time. The focus is on what samples of writing might enable us to know and understand about learning and teaching this important dimension of literacy in current classrooms.

Organometallic chemistry of diphosphazanes. Part 26. Ruthenium hydride complexes of chiral and achiral diphosphazane ligands and asymmetric transfer hydrogenation reactions

The half-sandwhich ruthenium chloro complexes bearing chelated diphosphazane ligands, [(eta(5)-Cp)RuCl{kappa(2)-P,P-(RO)(2)PN(Me)P(OR)(2)}] [R = C6H3Me2-2,6] (1) and [(eta(5)-Cp*)RuCl{kappa(2)-P, P-X2PN(R)PYY'}] [R = Me, X = Y = Y' = OC6H5 (2); R = CHMe2, X-2 = C20H12O2, Y = Y' = OC6H5 (3) or OC6H4'Bu-4 (4)] have been prepared by the reaction of CpRu(PPh3)(2)Cl with (RO)(2)PN(Me)P(OR)(2) [R = C6H3Me2-2,6 (L-1)] or by the reaction of [Cp*RuCl2](n) with X2PN(R)PYY' in the presence of zinc dust. Among the four diastereomers (two enantiomeric pairs) possible for the "chiral at metal" complexes 3 and 4, only two diastereomers (one enantiomeric pair) are formed in these reactions. The complexes 1, 2, 4 and [(eta(5)-Cp)RuCl {kappa(2)-P,P-Ph2PN((S)-*CHMePh)PPhY)] [Y = Ph (5) or N2C3HMe2-3,5 (SCSPRRu)-(6)] react with NaOMe to give the corresponding hydride complexes [(eta(5) -Cp)RuH {kappa(2)-P,P-(RO)(2)PN(Me)P(OR)(2)}] (7), [(eta(5)-Cp*)RuH {kappa(2)-P,P'-X2PN(R)PY2)] [R = Me, X = Y = OC6H5 (8); R = CHMe2, X-2 = C20H12O2, Y = OC6H4'Bu-4 (9)] and [(eta(5) -Cp)RuH(kappa(2)-P, P-Ph2PN((S)-*CHMePh)PPhY)][Y =Ph (10) or N2C3HMe2-3,5 (SCSPRRu)(11a) and (SCSPSRu)-(11b)]. Only one enantiomeric pair of the hydride 9 is obtained from the chloro precursor 4 that bears sterically bulky substituents at the phosphorus centers. On the other hand, the optically pure trichiral complex 6 that bears sterically less bulky substituents at the phosphorus gives a mixture of two diastereomers (11a and 11b). Protonation of complex 7 using different acids (HX) gives a mixture of [(eta(5)- Cp)Ru(eta(2)-H-2){kappa(2)-P, P-(RO)(2)PN(Me)P(OR)(2))]X (12a) and [(eta(5)-Cp)Ru(H)(2){kappa(2)-P, P-(RO)(2)PN(Me)P(OR)(2)}]X (12b) of which 12a is the major product independent of the acid used; the dihydrogen nature of 12a is established by T, measurements and also by synthesizing the deuteride analogue 7-D followed by protonation to obtain the D-H isotopomer. Preliminary investigations on asymmetric transfer hydrogenation of 2-acetonaphthone in the presence of a series of chiral diphosphazane ligands show that diphosphazanes in which the phosphorus centers are strong pi-acceptor in character and bear sterically bulky substituents impart moderate levels of enantioselectivity. Attempts to identify the hydride intermediate involved in the asymmetric transfer hydrogenation by a model reaction suggests that a complex of the type, [Ru(H)(Cl){kappa(2)-P,P-X2PN(R)PY2)(solvent)(2)] could be the active species in this transformation. (c) 2007 Elsevier B.V. All rights reserved.

Hard Custom, Hard Dance : Social Organisation, (Un)Differentiation and Notions of Power in a Tabiteuean Community, Southern Kiribati

Hard Custom, Hard Dance: Social Organisation, (Un)Differentiation and Notions of Power in a Tabiteuean Community, Southern Kiribati is an ethnographic study of a village community. This work analyses social organisation on the island of Tabiteuea in the Micronesian state of Kiribati, examining the intertwining of hierarchical and egalitarian traits, meanwhile bringing a new perspective to scholarly discussions of social differentiation by introducing the concept of undifferentiation to describe non-hierarchical social forms and practices. Particular attention is paid to local ideas concerning symbolic power, abstractly understood as the potency for social reproduction, but also examined in one of its forms; authority understood as the right to speak. The workings of social differentiation and undifferentiation in the village are specifically studied in two contexts connected by local notions of power: the meetinghouse institution (te maneaba) and traditional dancing (te mwaie). This dissertation is based on 11 months of anthropological fieldwork in 1999‒2000 in Kiribati and Fiji, with an emphasis on participant observation and the collection of oral tradition (narratives and songs). The questions are approached through three distinct but interrelated topics: (i) A key narrative of the community ‒ the story of an ancestor without descendants ‒ is presented and discussed, along with other narratives. (ii) The Kiribati meetinghouse institution, te maneaba, is considered in terms of oral tradition as well as present-day practices and customs. (iii) Kiribati dancing (te mwaie) is examined through a discussion of competing dance groups, followed by an extended case study of four dance events. In the course of this work the community of close to four hundred inhabitants is depicted as constructed primarily of clans and households, but also of churches, work co-operatives and dance groups, but also as a significant and valued social unit in itself, and a part of the wider island district. In these partly cross-cutting and overlapping social matrices, people are alternatingly organised by the distinct values and logic of differentiation and undifferentiation. At different levels of social integration and in different modes of social and discursive practice, there are heightened moments of differentiation, followed by active undifferentiation. The central notions concerning power and authority to emerge are, firstly, that in order to be valued and utilised, power needs to be controlled. Secondly, power is not allowed to centralize in the hands of one person or group for any long period of time. Thirdly, out of the permanent reach of people, power/authority is always, on the one hand, left outside the factual community and, on the other, vested in community, the social whole. Several forms of differentiation and undifferentiation emerge, but these appear to be systematically related. Social differentiation building on typically Austronesian complementary differences (such as male:female, elder:younger, autochtonous:allotochtonous) is valued, even if eventually restricted, whereas differentiation based on non-complementary differences (such as monetary wealth or level of education) is generally resisted, and/or is subsumed by the complementary distinctions. The concomitant forms of undifferentiation are likewise hierarchically organised. On the level of the society as a whole, undifferentiation means circumscribing and ultimately withholding social hierarchy. Potential hierarchy is both based on a combination of valued complementary differences between social groups and individuals, but also limited by virtue of the undoing of these differences; for example, in the dissolution of seniority (elder-younger) and gender (male-female) into sameness. Like the suspension of hierarchy, undifferentiation as transformation requires the recognition of pre-existing difference and does not mean devaluing the difference. This form of undifferentiation is ultimately encompassed by the first one, as the processes of the differentiation, whether transformed or not, are always halted. Finally, undifferentiation can mean the prevention of non-complementary differences between social groups or individuals. This form of undifferentiation, like the differentiation it works on, takes place on a lower level of societal ideology, as both the differences and their prevention are always encompassed by the complementary differences and their undoing. It is concluded that Southern Kiribati society be seen as a combination of a severely limited and decentralised hierarchy (differentiation) and of a tightly conditional and contextual (intra-category) equality (undifferentiation), and that it is distinctly characterised by an enduring tension between these contradicting social forms and cultural notions. With reference to the local notion of hardness used to characterise custom on this particular island as well as dance in general, it is argued in this work that in this Tabiteuean community some forms of differentiation are valued though strictly delimited or even undone, whereas other forms of differentiation are a perceived as a threat to community, necessitating pre-emptive imposition of undifferentiation. Power, though sought after and displayed - particularly in dancing - must always remain controlled.

How Kings are Made, How Kingship Changes : A Study of Ritual and Ritual Change in Pre-Colonial Owamboland, Namibia

This study discusses the legitimacy basis of political power and its changes in historical African societies. It starts from Luc de Heusch s tenet that political power required a legitimacy basis of a spiritual kind, often formulated as sacred kingship. In ancient and pre-literate societies such kings were held to be responsible for the fertility of man, land and cattle. The king was a paradoxical figure, symbolising society, but standing above it, while simultaneously being its victim by being ritually killed at old age. This was also how Owambo sacred kings were conceived. De Heusch suggested that African kings derived their power over fertility from having been made sacred monsters in the rituals of installation. With the example of Owambo kingship, this study argues that the transgressive and monstrous aspect is only one of several dimension of a king s sacredness and brings out the nurturing and symbolically female aspect, identified but not analysed further by de Heusch. In the Owambo kingly installation a king-elect was made sacred, and part of it was that a link was ritually created to the early owners of the land. Their consent made it possible for the king to promote fertility and to appropriate power emblems needed for ruling. In the kingdom of Ondonga the early owners of the land were the spirits of early Bushman inhabitants and those of an early kingly clan, both neglected in public memory. The sacred dimension of kingship was further augmented when kings manipulated and appropriated rain rituals and initiation rituals, both of which were related to fertility. The study argues that even though there were aspects of the sacred monster in Owambo kingship, its manifestation was, in part, a distortion of the reciprocal aspect of kingship that was expressed in the homage paid to various ancestor spirits. A change in succession practices from ritual regicide to political assassination took place concomitant with the introduction of firearms, and this broke the sacrificial aspect of sacred kingship paving the way for a more predatory form of kingship while the sacred status of the king was retained.

ESR study of dibarium copper formate tetrahydrate Part II. Optical absorption and temperature dependence of spin-hamiltonian parameters

The variations in certain spin-Hamiltonian parameters of the Cu++ ion in dibarium copper formate tetrahydrate with temperature have been studied. Optical absorption investigations on single crystals of the salt at room temperature and 90° K. are reported. The results are discussed in terms of a model in which vibronic mixing of certain electron levels of the Cu++ ion play an important role.

Studies in the hydrolysis of metal ions -Part I.Copper

The hydrolysis of cupric ion has been studied at various ionic strengths (0·01, 0·05, 0·1 and 0·5 M). The results are analyzed employing 'core + links' theory, log-log plot, normalization plot, and extrapolation method for obtaining the pure mononuclear curve. The stability constants of Cu2(OH)2++, Cu3(OH)4++, Cu(OH)+ and Cu(OH)2 have been reported.