Catalytic hydrodechlorination of chlorobenzene over supported palladium catalyst in buffered medium

The catalytic hydrodechlorination (HDC) reaction, which is an attractive abatement process for chlorinated organic wastes, was studied over a magnetically recoverable supported Pd(0) catalyst. We investigated the most favorable reaction conditions under which to obtain the highest substrate conversion rates while preserving the catalyst properties and morphology. Sodium hydroxide, triethylamine and buffered solutions were used as proton scavengers in the HDC of chlorobenzene under mild conditions. It was observed that sodium hydroxide caused corrosion of the silica support, triethylamine in 2-propanol preserved the morphology of the catalyst which could be recycled for up to five successive H DC reactions, and aqueous buffer solutions preserved the catalyst morphology and the catalytic activity for up to four successive HDC reactions. The use of buffer solutions to neutralize the HCl formed during the HDC reaction is an interesting, less aggressive, alternative approach to HDC reactions. (C) 2010 Elsevier B.V. All rights reserved.

Synthesis, characterization and cytotoxic activities of the [RuCl(2)(NO)(dppp)(L)]PF(6) complexes

The synthesis and characterization of ruthenium compounds of the type [RuCl(2)(NO)(dppp)(L)]PF(6) [dppp = 1,3-bis(diphenylphosphino)propane; L = pyridine, 4-methylpyridine, 4-phenylpyridine and dimethyl sulfoxide] are described. The complexes were characterized by elemental analysis, UV/Vis and infrared spectroscopy, cyclic voltammetry, and X-ray crystallography for the complexes with the pyridine and 4-methylpyridine ligands. In vitro evaluation of these nitrosyl complexes revealed cytotoxic activity from 7.1 to 19.0 mu M against the MDA-MB-231 breast tumor cells and showed that, in this case, they are more active than the reference metallodrug cisplatin. The 1,3-bis(diphenylphosphino)propane and the N-heterocyclic ligands alone failed to show cytotoxic activities at the concentrations tested (maximum concentration utilized = 200 mu M). (C) 2009 Elsevier Inc. All rights reserved.

Colonisation by epibionts and meiofauna of real and mimic pneumatophores in a cool temperate mangrove habitat

The size and pace of change in meiofaunal assemblages suggest that meiofauna make excellent subjects for testing theories about how ecological communities change. A field experiment was performed in which the  abundance and composition of epibionts and meiofauna on natural,  transplanted and mimic pneumatophores were monitored over a 47 wk period. Meiofaunal density increased with growth of algal epibionts, both reaching maximum values after 24 wk, at the end of winter. At this time the assemblages from the 3 substrata were similar, although the combined abundances of meiofauna on transplants and mimics were only 28% of the average on natural pneumatophores. Meiofaunal abundance on all substrata decreased rapidly during spring as algal cover declined due to desiccation. Twenty-three species of nematode were recorded from mimics compared with 8 and 7 from transplants and pneumatophores, respectively. A temporal sequence of feeding groups occurred in the order of epigrowth feeders, deposit feeders, and omnivore/predators, with the latter 2 adding to rather than replacing earlier trophic groups. Scavengers were found only on natural pneumatophores. The turnover rates of nematode species between all census times were similar, peaking at 63%, but there was no trend in the turnover rates with time. We conclude that mimics are more suitable than transplanted pneumatophores for colonisation studies because of their greater persistence and more easily standardised surface area. Moreover, the composition of colonising assemblages on them closely resembled assemblages on natural pneumatophores at the time of peak meiofaunal abundance.

Qualitative methods in early-phase drug trials : data and methods from a trial of N-acetylcysteine in schizophrenia

Objective: The pharmacokinetic profile of a drug often gives little indication of its potential therapeutic application, with many therapeutic uses of drugs being discovered serendipitously while being studied for different indications. As hypothesis-driven, quantitative research methodology is exclusively used in early-phase trials, unexpected but important phenomena may escape detection. In this context, this study aimed to examine the potential for integrating qualitative research methods with quantitative methods in early-phase drug trials. To our knowledge, this mixed methodology has not previously been applied to blinded psychopharmacologic trials.

Method: We undertook qualitative data analysis of clinical observations on the dataset of a randomized, double-blind, placebo-controlled trial of N-acetylcysteine (NAC) in patients with DSM-IV-TR–diagnosed schizophrenia (N = 140). Textual data on all participants, deliberately collected for this purpose, were coded using NVivo 2, and emergent themes were analyzed in a blinded manner in the NAC and placebo groups. The trial was conducted from November 2002 to July 2005.

Results: The principal findings of the published trial could be replicated using a qualitative methodology. In addition, significant differences between NAC- and placebo-treated participants emerged for positive and affective symptoms, which had not been captured by the rating scales utilized in the quantitative trial. Qualitative data in this study subsequently led to a positive trial of NAC in bipolar disorder.

Conclusions: The use of qualitative methods may yield broader data and has the potential to complement traditional quantitative methods and detect unexpected efficacy and safety signals, thereby maximizing the findings of early-phase clinical trial research.

Myocardial ischemia-reperfusion injury, antioxidant enzyme systems, and selenium : A review

Coronary heart disease (CHD) remains the greatest killer in the Western world, and although the death rate from CHD has been falling, the current increased prevalence of major risk factors including obesity and diabetes, suggests it is likely that CHD incidence will increase over the next 20 years. In conjunction with preventive strategies, major advances in the treatment of acute coronary syndromes and myocardial infarction have occurred over the past 20 years. In particular the ability to rapidly restore blood flow to the myocardium during heart attack, using interventional cardiologic or thrombolytic approaches has been a major step forward. Nevertheless, while 'reperfusion' is a major therapeutic aim, the process of ischemia followed by reperfusion is often followed by the activation of an injurious cascade. While the pathogenesis of ischemia-reperfusion is not completely understood, there is considerable evidence implicating reactive oxygen species (ROS) as an initial cause of the injury.

ROS formed during oxidative stress can initiate lipid peroxidation, oxidize proteins to inactive states and cause DNA strand breaks, all potentially damaging to normal cellular function. ROS have been shown to be generated following routine clinical procedures such as coronary bypass surgery and thrombolysis, due to the unavoidable episode of ischemia-reperfusion. Furthermore, they have been associated with poor cardiac recovery post-ischemia, with recent studies supporting a role for them in infarction, necrosis, apoptosis, arrhythmogenesis and endothelial dysfunction following ischemia-reperfusion. In normal physiological condition, ROS production is usually homeostatically controlled by endogenous free radical scavengers such as superoxide dismutase, catalase, and the glutathione peroxidase and thioredoxin reductase systems. Accordingly, targeting the generation of ROS with various antioxidants has been shown to reduce injury following oxidative stress, and improve recovery from ischemia-reperfusion injury.

This review summarises the role of myocardial antioxidant enzymes in ischemia-reperfusion injury, particularly the glutathione peroxidase (GPX) and the thioredoxin reductase (TxnRed) systems. GPX and TxnRed are selenocysteine dependent enzymes, and their activity is known to be dependent upon an adequate supply of dietary selenium. Moreover, various studies suggest that the supply of selenium as a cofactor also regulates gene expression of these selenoproteins. As such, dietary selenium supplementation may provide a safe and convenient method for increasing antioxidant protection in aged individuals, particularly those at risk of ischemic heart disease, or in those undergoing clinical procedures involving transient periods of myocardial hypoxia.

Conservation gone to the dogs : when canids rule the beach in small coastal reserves

On most developed coastlines, dunes backing ocean beaches constitute an urbanised landscape mosaic containing remnant pockets of small conservation areas. Urbanised beaches are also prime sites for domestic dogs, known to be environmentally harmful in many other settings. It is unknown, however, whether small, protected parcels of dune are adequate for biological conservation and whether dogs compromise their functional conservation objectives. Here we examine, for two small (2 km ocean boundary) reserves in Eastern Australia abutting an urban area, whether such small reserves can continue to function as effective conservation instruments on ocean beaches, using scavenger community composition and efficiency to assess ecosystem function. Two non-native species of canids—domestic dogs (Canis lupus familiaris) and red foxes (Vulpes vulpes)—were ubiquitous and numerous inside conservation areas, to the point of having become the most abundant vertebrate scavengers at the beach-dune interface, outcompeting native scavengers for wave-cast carrion. Dogs and foxes have effectively supplanted raptors, normally abundant on non-urban beaches in the region, and other avian scavengers, as the principal consumers of animal carcasses both inside the declared reserves and at the urban beach. Whilst the ecological threats posed by foxes are widely and intensively addressed in Australia in the form of fox-control programs, dog controls are less common and stringent. Our data emphasize, however, that managing domestic dogs may be required to the same extent in order to maintain key forms and functions in coastal reserves situated close to urban areas.

N-Acetylcysteine improves mitochondrial function and ameliorates behavioral deficits in the R6/1 mouse model of Huntington's disease

Huntington's disease (HD) is a neurodegenerative disorder, involving psychiatric, cognitive and motor symptoms, caused by a CAG-repeat expansion encoding an extended polyglutamine tract in the huntingtin protein. Oxidative stress and excitotoxicity have previously been implicated in the pathogenesis of HD. We hypothesized that N-acetylcysteine (NAC) may reduce both excitotoxicity and oxidative stress through its actions on glutamate reuptake and antioxidant capacity. The R6/1 transgenic mouse model of HD was used to investigate the effects of NAC on HD pathology. It was found that chronic NAC administration delayed the onset and progression of motor deficits in R6/1 mice, while having an antidepressant-like effect on both R6/1 and wild-type mice. A deficit in the astrocytic glutamate transporter protein, GLT-1, was found in R6/1 mice. However, this deficit was not ameliorated by NAC, implying that the therapeutic effect of NAC is not due to rescue of the GLT-1 deficit and associated glutamate-induced excitotoxicity. Assessment of mitochondrial function in the striatum and cortex revealed that R6/1 mice show reduced mitochondrial respiratory capacity specific to the striatum. This deficit was rescued by chronic treatment with NAC. There was a selective increase in markers of oxidative damage in mitochondria, which was rescued by NAC. In conclusion, NAC is able to delay the onset of motor deficits in the R6/1 model of Huntington's disease and it may do so by ameliorating mitochondrial dysfunction. Thus, NAC shows promise as a potential therapeutic agent in HD. Furthermore, our data suggest that NAC may also have broader antidepressant efficacy.

Status and ecological effects of the world's largest carnivores

Large carnivores face serious threats and are experiencing massive declines in their populations and geographic ranges around the world. We highlight how these threats have affected the conservation status and ecological functioning of the 31 largest mammalian carnivores on Earth. Consistent with theory, empirical studies increasingly show that large carnivores have substantial effects on the structure and function of diverse ecosystems. Significant cascading trophic interactions, mediated by their prey or sympatric mesopredators, arise when some of these carnivores are extirpated from or repatriated to ecosystems. Unexpected effects of trophic cascades on various taxa and processes include changes to bird, mammal, invertebrate, and herpetofauna abundance or richness; subsidies to scavengers; altered disease dynamics; carbon sequestration; modified stream morphology; and crop damage. Promoting tolerance and coexistence with large carnivores is a crucial societal challenge that will ultimately determine the fate of Earth’s largest carnivores and all that depends upon them, including humans.

Invasive carnivores alter ecological function and enhance complementarity in scavenger assemblages on ocean beaches

Species composition is expected to alter ecological function in assemblages if species traits differ strongly. Such effects are often large and persistent for nonnative carnivores invading islands. Alternatively, high similarity in traits within assemblages creates a degree of functional redundancy in ecosystems. Here we tested whether species turnover results in functional ecological equivalence or complementarity, and whether invasive carnivores on islands significantly alter such ecological function. The model system consisted of vertebrate scavengers (dominated by raptors) foraging on animal carcasses on ocean beaches on two Australian islands, one with and one without invasive red foxes (Vulpes vulpes). Partitioning of scavenging events among species, carcass removal rates, and detection speeds were quantified using camera traps baited with fish carcasses at the dune–beach interface. Complete segregation of temporal foraging niches between mammals (nocturnal) and birds (diurnal) reflects complementarity in carrion utilization. Conversely, functional redundancy exists within the bird guild where several species of raptors dominate carrion removal in a broadly similar way. As predicted, effects of red foxes were large. They substantially changed the nature and rate of the scavenging process in the system: (1) foxes consumed over half (55%) of all carrion available at night, compared with negligible mammalian foraging at night on the fox-free island, and (2) significant shifts in the composition of the scavenger assemblages consuming beach-cast carrion are the consequence of fox invasion at one island. Arguably, in the absence of other mammalian apex predators, the addition of red foxes creates a new dimension of functional complementarity in beach food webs. However, this functional complementarity added by foxes is neither benign nor neutral, as marine carrion subsidies to coastal red fox populations are likely to facilitate their persistence as exotic carnivores.

Limited functional redundancy in vertebrate scavenger guilds fails to compensate for the loss of raptors from urbanized sandy beaches

Aim: Globally, urbanization is one of the most widespread, intense and ecologically destructive forms of landscape transformation, and it is often concentrated in coastal areas. Theoretically, species losses attributable to urbanization are predicted not to alter overall ecosystem function if functional redundancy (i.e. replacement of function by alternative species) compensates for such losses. Here, we test this expectation by measuring how coastal urbanization affects scavenger guilds on sandy beaches and whether changes in guild composition result either in an overall loss of scavenging efficiency, or in functional compensation under alternative guild structures, maintaining net ecosystem functioning. Location: Fourteen beaches along the east coast of Australia with variable levels of urbanization. Methods: Scavenging communities and rates of carrion removal were determined using motion-triggered cameras at the beach-dune interface. Results: A substantial shift in the community structure of vertebrate scavengers was associated with gradients in urbanization. Iconic and functionally important raptors declined precipitously in abundance on urban beaches. Importantly, other vertebrates usually associated with urban settings (e.g. dogs, foxes, corvids) did not functionally replace raptors. In areas where < 15% of the abutting land had been developed into urban areas, carcass removal by scavengers was often complete, but always > 70%. Conversely, on beaches bordering coastal cities with < 40% of natural vegetation remaining, two-thirds of fish carcasses remained uneaten by scavengers. Raptors removed 70-100% of all deployed fish carcasses from beaches with < 8% urban land cover, but this number dropped significantly with greater levels of urbanization and was not compensated by other scavenger species in urban settings. Main conclusions: There is limited functional redundancy in vertebrate scavenger communities of sandy beach ecosystems, which impacts the system's capacity to mitigate the ecological consequences of detrimental landscape transformations.

A problematização do lixo e dos catadores: estudos de caso múltiplo sobre políticas públicas sob uma perspectiva foucaultiana

Municipal government policies supporting recycling cooperatives at the start of the 1990s and in the first years of the current century have contributed to resemanticizing trash rather than improving the living conditions of the street scavengers in the city of Rio de Janeiro. This idea was based on multiple case studies conducted in three post-consumption recycling cooperatives which have resulted from such policies. Interviews were held with three municipal government managers and 66 scavengers between 2002 and 2004, during a period of field observation that varied from two to six months in each case. Following a Foucaultian analysis approach, in this thesis post-consumption trash is considered as a discursive production. For this reason, the discourses have been analyzed (through an archaeology and a genealogy) that animated this object as a target condition of public policies. Thus, problematization of the trash has been proposed ¿ characterized by the concomitance of discourses related to an environmental and economic issue surrounding it, which would have impacted the scavengers' work. This proposal made it possible to consider the conditions that enable the scavengers to participate in this discursive production concerning trash. Problematization means the social enhancement of trash (its resemantization as recyclable) and the government policies were an attempt to make the scavengers adapt to this conjuncture. The conditions have been investigated that enable the scavengers to participate in the construction process of the discourse concerning trash (preparation of the strategies), in consonance with public policies. According to the three organizations observed, the public managers assumed that it would be possible for the scavengers to participate in the rules of discourse on trash, when they achieved economy of scale and when they sold to middlemen. Through the findings of the studies, however, it has been concluded that the ways in which these three organizations were managed enabled the scavengers to accede to the rules of discourse regarding problematized trash only when they could control the strategies that allow them to attend what is set by such rules.

Hierarquia, igualdade e diferença : lutas por reconhecimento no sul do Brasil

Este estudo busca investigar as lógicas da ação em cooperativas de produção e associações de catadores de lixo no bojo de processos de reestruturação econômica que não somente precarizam as condições de emprego, mas também implicam em processos de desassalariamento da força de trabalho. Tomando como perspectiva analítica a sociologia da experiência de François Dubet, decompomos as lógicas da ação de trabalhadores com inserção social distinta, ou seja, um primeiro grupo caracterizado por uma cultura operária e sindical e um segundo grupo caracterizado por um processo de dissociação em relação ao mundo do trabalho formal. Neste sentido, procurou-se investigar: a) as formas de inserção e integração sociais configuradas pelas relações de solidariedade, b) a dimensão da racionalidade estratégica de cada grupo traduzida nas lutas por reconhecimento, e, c) os processos de subjetivação expressos na afirmação identitária de cada coletivo de trabalhadores. Ou seja, quais as condições de possibilidade da ruptura com as hierarquias que organizam e estruturam o universo de coletivos de trabalhadores com origens sociais tão diversas quando confrontados com o princípio meta-social da igualdade? Noutras palavras, quando compelidos com a necessidade de organizar uma cooperativa ou associação, enquanto alternativa palpável de subsistência, os trabalhadores se deparam com um contexto bem diverso da situação de assalariamento. Com efeito, a experiência associativa irá implicar que a adesão à cooperativa ou associação deve ser livre e voluntária e que a gestão e os processos de deliberação devem ser democráticos. A partir da pesquisa de campo verificou-se um processo de subjetivação marcado por estratégias distintas nas cooperativas e associações: enquanto nas cooperativas a adesão dos trabalhadores era caracterizada por uma certa ambivalência entre o compromisso com o projeto de construção da cooperativa e uma postura pautada por um certo pragmatismo tipificado por um campo de possíveis restrito no tocante as alternativas de inserção social, nas associações de catadores de lixo verificou-se um processo de ruptura com os padrões de sociabilidade primária acentuadamente hierarquizados a partir da participação das mulheres nas associações, bem como um efetivo compromisso com o projeto associativo. Na esfera da ação coletiva, a constituição de cooperativas a partir de empresas em situação falimentar revelou uma nova estratégia sindical marcada por uma ação defensiva ante os processos de reestruturação econômica que eliminam postos de trabalho. Já, na ação coletiva das associações constatou-se um movimento de luta pelo reconhecimento de direitos e recuperação da cidadania. Tal movimento é caracterizado por uma lógica do respeito possuindo uma dupla inflexão, ou seja, por um lado busca romper no âmbito da esfera privada com a dominação masculina expressa num código de honra, cuja conseqüência mais dramática se traduz na violência doméstica, e por outro lado se constata um movimento em direção à esfera pública a partir da articulação de uma associação com um movimento social traduzindo desta maneira a reivindicação pelo reconhecimento da dignidade de indivíduos sujeitos a todo tipo de reconhecimento recusado.

Avaliação in vitro e in vivo da Atividade Antioxidante do Extrato Hidroetanólico de Folhas de Turnera ulmifolia Linn. var. elegans (Turneraceae)

Recently, it has been a increasing interest in the antioxidative role of natural products to aid the endogenous protective biological systems against the deleterious effects of oxygen (ROS) and nitrogen (RNS) reactive species. Many antioxidant compounds, naturally occurring from plant sources. Natural antioxidants can protect and prevent the human body from oxidative stress and retard the progress of many diseases in which free radical are involved. Several plants used in the folk medicine to treat certain disorders that are accompanied by inflammation and other pharmacological properties have been proved their attributed properties, such antioxidant activity. Turnera ulmifolia Linn. var. elegans (Turneraceae), frequently employed by population as a medicinal plant, demonstrated antioxidant activity by in vitro and in vivo assays, using its leaf hydroethanolic extract (10%) he in vitro DPPH radical-scanvenging activity showed a strong antioxidant activity (86.57% ± 0.14), similar to Carduus marianus and catequine effects. For the in vivo assays, adult female Wistar rats (n=48) with carbon tetrachloride hepatic injury induced (2,5mL/kg i.p.) were used, Six groups or rats were uses (n=8) [G1 = control (1,25 mL/kg i.p. vehicle); G2 = CCl4 (2,5 mL/kg i.p.); G3 = CCl4 + extract 7 days (500 mg/kg p.o.); G4 = CCl4 + Legalon® 7 days (50 mg/kg p.o.), G5 = CCl4 + extract 21 days (500 mg/kg p.o.) e G6 = CCl4 + Legalon® 21 days (50 mg/kg p.o.)]. The hepatic oxidative injury was evaluated through biochemical parameters [alanine amino transferase (ALT), aspartate amino transferase (AST)] histopathological study, while thiobarbituric acid reactive products (TBAR), glutathione (GSH), catalase (CAT), superoxide dismutase (SOD), and glutathione peroxidase (GPx) levels were used to evaluate proantioxidant parameters. The plant extract tested was found effective as hepatoprotective as evidenced by a decreasing in the ALT and AST activities (p<0.001) and TBAR (plasma, p<0.001 and liver, p<0.001). Levels of GSH (blood, p<0.001 and liver, p<0.001) and antioxidant enzymes [CAT erythrocyte (p<0.05) and hepatic (p<0.01); SOD erythrocyte (p<0.001) and hepatic (p<0.001); GPx erythrocyte (p<0.001) and hepatic (p<0.001)] were also significantly increased. Histopathological changes induced by CCl4 were significantly reduced by the extract treatment. The data obtained were comparable to that of Legalon®, a reference hepatoprotective drug. The results showed that T. ulmifolia leaf extract protects against CCl4 induced oxidative damage. Therefore, this effect must be associated to its antioxidant activity, attributed to the phenolic compounds, present in these extract, which can act as free radical scavengers