Synthesis, structural characterization and electrochemical activity of oxidovanadium(IV/V) complexes of a diprotic ONS chelating ligand

The present work reports the chemistry of a few oxidovanadium(IV) and (V) complexes of the ONS chelating ligand S-benzyl-beta-N-(2-hydroxyphenylethylidine) dithiocarbazate (H2L). Major objective of this work is to arrive at some general conclusions about the influence of binding environment generated by the replacement of an O-donor center by a S-donor point in a ligand (of a similar arrangement of the other O- and N-donor points) on the redox behavior and on the structural features of comparable [VO(OEt)(ONS)] and [VO(OEt)(ONO)] complexes. Synthesis, characterization by various physicochemical techniques (UV-Vis, IR, EPR and elemental analysis), exploration of electrochemical activity of the oxidovanadium(V) complex [(VO)-O-V(OEt) L] (1), the mixed ligand complex [(VO)-O-V(N-O)L] (3) (where N-O is the mono anion of 8-hydroxyquinoline) and a binuclear complex [(VO)-O-V(OEt)L](2)(mu-4,4'-bipy) (2) are reported. Similar studies on of mixed ligand oxidovanadium(IV) complexes of the formula [(VO)-O-V(N-N)L] (4,5) (where N-N = 2,2'-bipy and o-phen) are also presented here. The [(VO)-O-V(OEt)L] complex is pentacoordinated and distorted square pyramidal, while the [V-IV(N-N)L] complexes are hexacoordinated and octahedral. Structural features of the complex 1 were compared with the corresponding aspects of the previously reported analogous complex [(VO)-O-V(OEt)(ONO)] (1').

The Spanish Ambassador and Samuel Daniel's Vision of the Twelve Goddesses: A New Document [with text]

The performance of Samuel Daniel's masque The Vision of the Twelve Goddesses at court on January 8, 1604 took place in the midst of the preliminary negotiations that would lead to the signing of the Anglo-Spanish peace at Somerset House the following August. Philip III sent a special ambassador to England to congratulate James on his accession, and a series of tussles between Juan de Tassis and his French counterpart ensued. As a recently-discovered document in the Archivo General de Simancas reveals, Anna of Denmark intervened personally to insure that de Tassis, and not the Frenchman, attended the masque. This was a clear signal of James and Anna's peace aims, which de Tassis conveyed to the King of Spain; moreover, he enclosed in his dispatch a text of Daniel's masque which he clearly considered both political intelligence and of interest to the theater-loving Hapsburg monarch. The Simancas text of the Daniel masque is a new version, hitherto unknown, which adds to our knowledge of the circumstances in which the first Stuart masque was performed. Here we present a transcription and annotated translation of both de Tassis' letter and the text of the masque he had compiled for Philip III. (B. C.-E. and M. H.)

Transnational urbanism in Port of Spain: returning middle-class urban elites

Port of Spain, Trinidad offers an ideal context in which to analyze pre-retirement return migration to a Global South urban realm, expanding transnational urban research beyond the conventional focus on Global North metropolitan destinations. In this article, we draw on the transnational narratives of a selected sample of relatively youthful Trinidadians, who have spent many years abroad acquiring education and professional experience, but who have then decided to return in mid-career to the capital region of the island nation of their birth, or of their parent(s). Theoretically, we position these returning professionals as members of a "middling" transnational urban class whose return is at least partly motivated by a desire to "make a difference." Our results contribute to a growing literature that documents the role of transnational middle-class urban elites returning elsewhere in the Carribbean: "middling" transnational urbanism is reshaping key facets of urbanization in the Global South.

Synthesis, chemical, electrochemical characterization of oxomolybdenum(V) complexes of 2-(3,5-dimethyl pyrazol-1-yl) benzothiazole ligand: crystal structure of ligand and oxomolybdenum(VI) complex and density functional theory (DFT) calculation

This work reports the ligational behavior of the neutral bidentate chelating molecule 2-(3,5-dimethyl pyrazol-1-yl) benzothiazole towards the oxomolybdenum(V) center. Both mononuclear complexes of the type (MoOX3L)-O-V and binuclear complexes of the formula (Mo2O4X2L2)-O-V (where X = Cl, Br) are isolated in the solid state. The complexes are characterized by elemental analyses, various spectroscopic techniques (UV-Vis IR), magnetic susceptibility measurement at room temperature, and cyclic voltammetry for their redox behavior at a platinum electrode in CH3CN. The mononuclear complexes (MoOX3L)-O-V are found to be paramagnetic while the binuclear complexes Mo2O4X2L2 are diamagnetic. Crystal and molecular structure of the ligand and the dioxomolybdenum complex (MoO2Br2L)-O-VI (obtained from the complex MoOBr3L during crystallization) have been solved by single crystal X-ray diffraction technique. Relevant DFT calculations of the ligand and the complex (MoO2Br2L)-O-VI are also carried out.

Oxovanadium(IV) and (V) complexes of acetylpyridine-derived semicarbazones exhibit insulin-like activity

Reaction of 2-acetylpyridine semicarbazone (H2APS), 3-acetylpyridine semicarbazone (H3APS) and 4-acetylpyridine semicarbazone (H4APS) with [VO(acac)(2)] (acac = acetylacetonate) gave [VO(H2APS)(acac)(2)] (1), (VO(H3APS)(acac)(2)] (2) and [VO(4APS)(acac) (H2O)] center dot 1/2H(2)O (3). Oxidation of complex 1 in acetonitrile gave [VO2(2APS)] (4). The crystal structures of complexes 1 and 4 have been determined. Complexes 1-3 were able to enhance glucose uptake and to inhibit glycerol release from adipocytes, which indicate their potential to act as insulin-mimics. (C) 2008 Elsevier Ltd. All rights reserved.

PANA V : Evaluation of a Literacy Project

PANA V Evaluation of a Literacy ProjectSUMMARY AND CONCLUSIONSThis evaluation set out to explore the impact of the literacy work carried out through PANA V. It focussed on clarifying effects such as empowerment and poverty reduction in relation to the civil society. Two specific objectives were to evaluate the methodological approach and the didactic materials and to evaluate the sustainability of the project.Although the focus of the evaluation has been PANA V, the project has been evaluated in its context, as one in a series of five projects located in Rwanda ten years after the war and genocide. The conclusion will consider future plans in this field.The evaluator has striven to create a holistic picture of the effects of the project, although the given time for the evaluation was short. Only three weeks were spent in the field study and only ten days in the actual field. Although there were some organisational and logistic problems, as is common when carrying out a study like this in a poor country, many literacy sites were visited and quite many participators were interviewed. The overall impression from the study is overwhelmingly positive. So many people commit themselves in this task of teaching Rwandans reading, writing and numeracy. Despite harsh conditions learners strive to learn and group leaders devote themselves to the task. Many leaders on different levels try their very best to manage their difficult and demanding task. The main objective was to explore the impact of the project on poverty reduction, particularly on empowerment and strategies for everyday life. Women were to be regarded particularly. From the results it is clear that the project has a strong, positive impact both on poverty reduction and empowerment of marginalised groups. Among those who have benefited from the alphabetisation are mainly women. Unfortunately, when it comes to leaders in PANA, who may also be said to have benefited from the project, only a small minority is women. This is something that is recommended that it be reconsidered inside the organisation. As a majority of the targeted learners are women, and as the economic and social situation of women in Rwanda is generally weak, this is a question that I recommend the Pentesostal church and ADEPR to look particularly into. With many women being single breadwinners of their households, it is important that also women get access to positions that may bring benefits of different kind.It is also clear that the project has positive effects for the civil society. In the present situation in Rwanda, during the process of reconciliation and rapid progress, basic education for the poor majority is a democratic issue. In a country with a plethora of internet-cafés in the capital and a small minority that use cars and mobile-telephones to communicate nation-wide, it is of outmost importance that the majority acquires basic education, of which literacy is a central part. To strengthen the civil society in Rwanda literacy is important. One central issue is then that Rwanda develops toward becoming a country where literacy is used for the benefit of the citizens and it is a democratic issue that all citizens get an opportunity to participate. Crucial for this is that strong efforts are put into primary schools nation-wide. Literacy projects for adults, like PANA, may only complement these efforts, but they constitute important and necessary complements. Other relevant ways to promote literacy are campaigns in Radio and TV and through cultural events such as festivals, music and theatre. News papers, magazines and books are natural parts of such campaigns as well as adult education. As stated under the results not much can be said about the didactics in this evaluation. On the whole the methodology and the materials fill their function well and receive a high reputation. As people learn to read and write under very simple conditions, obviously the approach is appropriate. A few suggestions may be given from the study:•Focus groups leaders’ attention on clearness, that they show very clearly what is to be read. Good structuring is probably of great importance for many learners.•Make clear what is tested in the tests and consider the possibility to use a holistic test that would be more congruent with the methodology. The possibility to use only one grade, pass, would enable a more practical test, such as reading a short, relevant text, writing something relevant and solving practical mathematic problems. Avoid tests that demand school knowledge.•Avoid using methaphors such as “fight against illiteracy” and connections between illiteracy/literacy and darkness/light. It is not true that illiteracy causes bad things and that literacy only brings good. •Be prepared that it may be more difficult in the future to achieve the goals as it may be the case that the early learners where the ones who achieved easily. The goal of “literacy in six month” in PANA will probably hold only for some learners but also those who do not manage in six months need literacy skills.A third objective was to secure sustainability. As for sustainability of the project in itself, and of the literacy process, the main conclusion is that there is a good potential. The commitment and devotedness among many involved in PANA proves good. One weakness is individual leaders in ADEPR who do not see this as an important task for the Pentecostal church in Rwanda. Other weaknesses are the unwillingness to mention explicitly the wish, for example among group leaders, to get some kind of incentive and the fear of loosing believers by cooperation with other organisations. A higher degree of transparency in this issue would probably solve some irritations and tensions.As for the sustainability of the literacy skills much may be done to improve. The acquired skills seem to be comparably relevant. The level achieved, and the level tested, may be defined as basic literacy skills, consisting of basic reading, writing and numeracy skills. However, these skills are very restricted and there is a high risk that the skills will decline, which means that there is a high risk that people will forget how to read and write because of lack of exercising. From these conclusions a few suggestions for future development will be given.

Attitudes towards the minority variety Caló in the south of Spain : a sociolinguistic study

Caló is a variety spoken by the Spanish Calé (i.e. the Roma). It belongs to a group of languages referred to as “Para-Romani”, characterized by Romani vocabulary, but largely non-Romani morphology, phonology and syntax, in the case of Caló deriving from Spanish. According to previous research carried out – with focus on the vocabulary and the grammar of this variety – Caló is on its way to extinction. However, there is an expressed interest in reintroducing a form called “Romanó-Caló”. Attitudes play an important role in minority language maintenance as well as in order for a revitalization project to be successful. The aim of this study is to measure the attitudes that both Calé and non-Calé have towards Caló and Caló speakers, a type of study never carried out in the past. The methods applied are both direct and indirect. In total, 231 informants listened to different recordings of voices acting as either a “Spanish speaking person” or a “Caló speaking person”, a technique referred to as ‘matched guise’, answering questions related to the voices on attitude scales. Furthermore, 182 of the informants rated their agreement or disagreement to positive and negative items towards Caló and its speakers on a Likert scale. The results of the analysis indicate that the attitudes differ towards Caló and Caló speakers, depending on the informant’s (a) ethnicity (b) contact with Caló as well as with Caló speakers, and (c) gender. It is those who – in their own opinion – belong to the ethnic group Calé, as well as those who claim that they have some contact with the variety and its speakers, who show positive attitudes in both parts of the study. The women also show more positive attitudes than the men. It is also possible to note positive attitudes towards the variety and its speakers among the subjects with a high level of knowledge of Caló words, as well as among those with the highest willingness to use Caló. These observations suggest that a revitalization project of the variety Caló has a clear chance of being successful.

Osborne v Estate of Osborne: an equitable agreement or a contract in law: merely a matter of nomenclature?

It has been more than lOO years since the leading case on mutual wills was handed down in Dufour v Pereira. Despite the passage of time. there continues to be a comparative dearth of modern authority), on this type of will. This area of the law was. however. recently considered by the Victorian Court of Appeal in Osborne. This case note evaluates Osborne in light of the relevant grounds of appeal. It is ultimately concluded that Osborne was very much a lost opportunity. The grounds of appeal raised many key issues pertaining to both the substantive law and evidential aspects of mutual wills. However the Court of Appeal did not take the opportunity to articulate clearly its views of the relevant law.