Synthesis and characterization of mono- and bis-ligand zinc(II) and cadmium(II) complexes of the di-2-pyridylketone Schiff base of S-benzyl dithiocarbazate (Hdpksbz) and the X-ray crystal structures of the [Zn(dpksbz)2] and [Cd(dpksbz)NCS]2 complexes

New mono- and bis-chelated zinc(II) and cadmium(II) complexes of formula, [M(dpksbz)NCS] (dpksbz = anionic form of the di-2-pyridylketone Schiff base of S-benzyldithiocarbazate) and [M(dpksbz)(2)] (M = Zn-II, Cd-II) have been prepared and characterized. The structure of the bis-ligand complex, [Zn(dpksbZ)(2)] has been determined by X-ray diffraction. The complex has a distorted octahedral geometry in which the ligands are coordinated to the zinc(II) ion as uninegatively charged tridentate chelates via the thiolate sulfur atoms, the azomethine nitrogen atoms and the pyridine nitrogen atoms. The distortion from a regular octahedral geometry is attributed to the restricted bite angles of the Schiff base ligands. X-ray structural analysis shows that the [Cd(dpksbz)NCS](2) complex is a centrosymmetric dimer in which each of the cadmium(II) ions adopts a five-coordinate, approximately square-pyramidal configuration with the Schiff base acting as a tetradentate chelating agent coordinating a cadmium(II) ion via one of the pyridine nitrogen atoms, the azomethine nitrogen atom and the thiolate sulfur atom; the second pyridine nitrogen atom is coordinated to the other cadmium(II) ion of the dimer. The fifth coordination position around each cadmium(II) is occupied by an N-bonded thiocyanate ligand. (C) 2003 Elsevier Science Ltd. All rights reserved.

Reforming the law of medical negligence: Solutions in search of a problem

The Commonwealth Government's Principles Based Review of the Law of Negligence recently recommended reforms aimed at limiting liability and damages arising from personal injury and death, in response to the growing perception that the current system of compensating personal injury had become financially unsustainable. Recent increases in medical liability and damages have eroded the confidence of doctors and their professional bodies, with fears of unprecedented desertion from and reduced recruitment into high risk areas, and one of the primary foci of the review concerned medical negligence. The article analyses proposals to redefine the principles necessary for the finding of negligence, against the terms of reference of the review. The article assumes that for the foreseeable future, Australia will persist with tort-based compensation for personal injury rather than developing a no-fault scheme. If the suggested changes to the fundamental principles of negligence are unlikely to reduce medical liability, greater attention might be given to the processes which come into play after the finding of negligence, where reform is more likely to benefit both plaintiffs and defendants.

A global health problem caused by arsenic from natural sources

Arsenic is a carcinogen to both humans and animals. Arsenicals have been associated with cancers of the skin, lung, and bladder. Clinical manifestations of chronic arsenic poisoning include non-cancer end point of hyper- and hypo-pigmentation, keratosis, hypertension, cardiovascular diseases and diabetes. Epidemiological evidence indicates that arsenic concentration exceeding 50 mug l(-1) in the drinking water is not public health protective. The current WHO recommended guideline value for arsenic in drinking water is 10 mug l(-1), whereas many developing countries are still having a value of 50 mug 1(-1). It has been estimated that tens of millions of people are. at risk exposing to excessive levels of arsenic from both contaminated water and arsenic-bearing coal from natural sources. The global health implication and possible intervention strategies were also discussed in this review article. (C) 2003 Elsevier Ltd. All rights reserved.

Cytotoxic iron chelators: Characterization of the structure, solution chemistry and redox activity of ligands and iron complexes of the di-2-pyridyl ketone isonicotinoyl hydrazone (HPKIH) analogues

Di-2-pyridyl ketone isonicotinoyl hydrazone (HPKIH) and a range of its analogues comprise a series of monobasic acids that are capable of binding iron (Fe) as tridentate (N,N,O) ligands. Recently, we have shown that these chelators are highly cytotoxic, but show selective activity against cancer cells. Particularly interesting was the fact that cytotoxicity of the HPKIH analogues is maintained even after complexation with Fe. To understand the potent anti-tumor activity of these compounds, we have fully characterized their chemical properties. This included examination of the solution chemistry and X-ray crystal structures of both the ligands and Fe complexes from this class and the ability of these complexes to mediate redox reactions. Potentiometric titrations demonstrated that all chelators are present predominantly in their charge-neutral form at physiological pH (7.4), allowing access across biological membranes. Keto-enol tautomerism of the ligands was identified, with the tautomers exhibiting distinctly different protonation constants. Interestingly, the chelators form low-spin (diamagnetic) divalent Fe complexes in solution. The chelators form distorted octahedral complexes with Fe-II, with two tridentate ligands arranged in a meridional fashion. Electrochemistry of the Fe complexes in both aqueous and non-aqueous solutions revealed that the complexes are oxidized to their ferric form at relatively high potentials, but this oxidation is coupled to a rapid reaction with water to form a hydrated (carbinolamine) derivative, leading to irreversible electrochemistry. The Fe complexes of the HPKIH analogues caused marked DNA degradation in the presence of hydrogen peroxide. This observation confirms that Fe complexes from the HPKIH series mediate Fenton chemistry and do not repel DNA. Collectively, studies on the solution chemistry and structure of these HPKIH analogues indicate that they can bind cellular Fe and enhance its redox activity, resulting in oxidative damage to vital biomolecules.

Unraveling the barriers to reconceptualization of the problem in chronic pain: The actual and perceived ability of patients and health professionals to understand the neurophysiology

To identify why reconceptualization of the problem is difficult in chronic pain, this study aimed to evaluate whether (1) health professionals and patients can understand currently accurate information about the neurophysiology of pain and (2) health professionals accurately estimate the ability of patients to understand the neurophysiology of pain. Knowledge tests were completed by 276 patients with chronic pain and 288 professionals either before (untrained) or after (trained) education about the neurophysiology of pain. Professionals estimated typical patient performance on the test. Untrained participants performed poorly (mean +/- standard deviation, 55% +/- 19% and 29% +/- 12% for professionals and patients, respectively), compared to their trained counterparts (78% +/- 21% and 61% +/- 19%, respectively). The estimated patient score (46% +/- 18%) was less than the actual patient score (P < .005). The results suggest that professionals and patients can understand the neurophysiology of pain but professionals underestimate patients' ability to understand. The implications are that (1) a poor knowledge of currently accurate information about pain and (2) the underestimation of patients' ability to understand currently accurate information about pain represent barriers to reconceptualization of the problem in chronic pain within the clinical and lay arenas. (C) 2003 by the American Pain Society.

Sistema integrado de passagens e di??rias: SIPAD

O Sistema Integrado de Passagens e Di??rias (SIPAD), foi concebido no conceito de integra????o de dados e utiliza uma base de dados ??nica que evita o retrabalho e a inconsist??ncia de informa????es. O sistema tem por objetivo tornar mais ??gil, transparente e desburocratizado o processo de solicita????o, gerenciamento e controle de passagens e di??rias no ??mbito do Minist??rio da Sa??de. O SIPAD permite, em tempo real, o atendimento dos pedidos de viagens mediante requisi????es eletr??nicas com alto grau de confiabilidade e seguran??a. O sistema permite ainda o controle f??sico e a gest??o financeira de todos os pedidos de viagem; o c??lculo autom??tico de valores de di??rias inclusive em moeda estrangeira; o acompanhamento de trechos de viagens e conex??es internacionais com indica????o dos aeroportos; o controle e presta????o de contas de viagens; o desconto autom??tico do valor do vale refei????o por UF. A seguran??a do SIPAD ?? garantida por sistema que permite acessos escalonados por n??veis de senha , a partir de perfis previamente definidos. No SIPAD pode-se realizar consultas on line e emiss??o automatizada de relat??rios operacionais e gerenciais com interface gr??fica. Os resultados ap??s a implanta????o , em 01/07/99, j?? causam impactos significativos. A economia estimada para o ano 2000, apenas em uma unidade gestora do Minist??rio, ?? de redu????o de 113.606 folhas de papel; elimina????o de 23.346 etiquetas; elimina????o de 40.468 assinaturas de gestores e ordenadores de despesa; elimina????o de 58.369 procedimentos de carimbo em pap??is; elimina????o de 11.673 registros de controle e 58.459 tramita????es de documentos

Sistema informatizado de controle de di??rias

O projeto consiste na automa????o de todo o processo de elabora????o, c??lculo, concess??o e pagamento de di??rias possibilitando ainda a an??lise da execu????o or??ament??ria e financeira, por meio de um sistema informatizado de controle. Este sistema ?? ??gil e de f??cil opera????o, e confere seguran??a de acesso ??s informa????es. Ele opera em ambiente de rede, de maneira que qualquer setor possa controlar suas di??rias, utilizando-se de um ??nico banco de dados instalado em um computador servidor

Di??logo, entendimento, negocia????o: voc?? est?? preparado?

O acordo conciliador t??o discutido hoje na pol??tica e na economia n??o se limita a estes setores. Objetivos conflitantes ocorrem nas rela????es entre pessoas em todos os n??veis hier??rquicos de qualquer administra????o. A quest??o ?? o como transform??-los em objetivos maiores e unificadores ou em pactos que possibilitem a conviv??ncia e o desenvolvimento de grupos com interesses opostos. As habilidades de negocia????o emergem, a??, como o instrumental adequado para prevenir e administrar conflitos. E os bons negociadores n??o resultam da transa????o improvisada ou da genialidade mas, da a????o programada, da pesquisa e an??lise de situa????o, do auto-conhecimento e do conhecimento do outro, do esfor??o orientado

A for??a propulsora do di??logo social

Lideran??as sindicais, empresariais, sociais, al??m de intelectuais, acad??micos e representantes de variados setores, t??m trabalhado desde 2003 em uma proposta inovadora: pensar o Brasil que se deseja e, a partir da??, apresentar ao presidente da Rep??blica indica????es do rumo para tornar o Pa??s socialmente justo e economicamente sustent??vel. Essa ?? a tarefa do Conselho de Desenvolvimento Econ??mico e Social (CDES), composto por 90 pessoas da sociedade civil e 13 ministros, que se constitui em espa??o de di??logo no qual a diversidade dos atores sociais, mais do que revelar a heterogeneidade da popula????o de um pa??s continental, possibilita ampliar os pontos de vista e os argumentos sobre temas da agenda nacional, enriquecendo o debate e qualificando as sugest??es para um projeto de desenvolvimento de longo prazo. Com o surgimento do CDES, a discuss??o de grandes temas deixou de ser uma conversa de pequenos grupos, com acesso ao presidente, para ser um exerc??cio pleno de representa????o dos diversos grupos, a maior parte dos quais n??o tinha canal para seus pleitos e demandas ao governo. ???N??o h?? mais vanguarda. O acesso e o fluxo de informa????o tornaram-se produtos de todos. Acabou a demanda de balc??o, a vis??o tradicional de um Conselho, que cooptava as pessoas para a defesa de determinadas id??ias. Agora o di??logo ?? sem rupturas. ?? um modo de trazer governan??a, criar consenso, estabelecer espa??o de converg??ncia???, diz a respons??vel pela Secretaria do Conselho de Desenvolvimento Econ??mico e Social (Sedes), Esther Bemerguy Albuquerque.

Gravitational waves : a 100-year tool applied to the dark energy problem

Recent observations from type Ia Supernovae and from cosmic microwave background (CMB) anisotropies have revealed that most of the matter of the Universe interacts in a repulsive manner, composing the so-called dark energy constituent of the Universe. Determining the properties of dark energy is one of the most important tasks of modern cosmology and this is the main motivation for this work. The analysis of cosmic gravitational waves (GW) represents, besides the CMB temperature and polarization anisotropies, an additional approach in the determination of parameters that may constrain the dark energy models and their consistence. In recent work, a generalized Chaplygin gas model was considered in a flat universe and the corresponding spectrum of gravitational waves was obtained. In the present work we have added a massless gas component to that model and the new spectrum has been compared to the previous one. The Chaplygin gas is also used to simulate a L-CDM model by means of a particular combination of parameters so that the Chaplygin gas and the L-CDM models can be easily distinguished in the theoretical scenarios here established. We find that the models are strongly degenerated in the range of frequencies studied. This degeneracy is in part expected since the models must converge to each other when some particular combinations of parameters are considered.

Brazil: an emerging military power? The problem of the use of force in Brazilian international relations in the 21st century

The central goal of this paper is thinking about the Brazilian military power and its linking to the international ambitions of the country in the 21st century. After a comparative analysis to other BRICs and with a historical one about Brazil's strategic irrelevance, we aim to establish what the minimum military capacity Brazil would need in order to meet the country's latest international interests. Similarly, it will be discussed if the National Strategy of Defense, approved in 2008, and the recent strategic agreements signed with France represent one more step toward this minimum military capacity.

Extracting and verifying coordination models from source code

Current software development relies increasingly on non-trivial coordination logic for com- bining autonomous services often running on di erent platforms. As a rule, however, in typical non-trivial software systems, such a coordination layer is strongly weaved within the application at source code level. Therefore, its precise identi cation becomes a major methodological (and technical) problem which cannot be overestimated along any program understanding or refactoring process. Open access to source code, as granted in OSS certi cation, provides an opportunity for the devel- opment of methods and technologies to extract, from source code, the relevant coordination information. This paper is a step in this direction, combining a number of program analysis techniques to automatically recover coordination information from legacy code. Such information is then expressed as a model in Orc, a general purpose orchestration language

On the Problem of Balancing the DC Capacitor Voltage Divider in Back-to-Back Multilevel Converters

This paper presents a new generalized solution for DC bus capacitors voltage balancing in back-to-back m level diode-clamped multilevel converters connecting AC networks. The solution is based on the DC bus average power flow and exploits the switching configuration redundancies. The proposed balancing solution is particularized for the back-to-back multilevel structure with m=5 levels. This back-to-back converter is studied working with bidirectional power flow, connecting an induction machine to the power grid.