Propriétés magnétiques et photomagnétiques d'un complexe macrocyclique à transition de Spin : un nouvel exemple de multi-metastabilité

Le phénomène de transition de spin correspond au changement d’état de spin d’un ion de transition sous l’action d’une perturbation extérieure (T, P, B, hv). Cette commutation ouvre de réelles perspectives dans le domaine de l’affichage et du stockage d’information. Ce travail présente, tout d’abord, l’étude d’un complexe macrocyclique heptacoordiné à transition de spin, noté [Fe(L222(N3O2)(CN)2)]•H 2O avec une sphère de coordination FeN3O2C2. L’examen attentif des propriétés magnétiques et structurales a permis de proposer un diagramme de phase expliquant la nature multi-métastable de ce système. Nous analysons et discutons l’influence de la température, des aspects cinétiques et de la photo-excitation sur les phases mises en jeu. Nous avons ensuite synthétisé divers analogues en tentant d’influer sur la géométrie du macrocycle (forme ouverte, accroissement de la rigidité), sur la nature de la sphère de coordination (substitution des atomes d’oxygène par des atomes de soufre et azote). Deux résultats majeurs ont été obtenus : une température limite record d’effet de trempe T(TIESST) de 171 K et une stabilité d’un état photo-induit avec un T(LIESST) de 110 K pour un composé totalement bas spin jusqu'à 440 K.The spin crossover phenomenon corresponds to the modification of a transition metal ion’s spin state under an external perturbation (T, P, B, hv). Such switches could be used as active elements in data storage and display devices. This work presents first the study of a macrocyclic spin crossover complex, [Fe(L222(N3O2)(CN)2)]•H2O with FeN3O2C2 coordination sphere. The detailed study of the magnetic and structural properties has led to propose a phase diagram which explains the multimetastable nature of the system. The influence of temperature, photo-excitation and kinetics are analysed and discussed for the involved phases. Secondly, several analogous complexes have been then synthesized in order to tune the macrocycle geometry (rigidity, open chains...) and the coordination sphere’s nature (replacement of the oxygen atoms by nitrogen and sulphur atoms). Two major results have been obtained: the highest temperature limit T(TIESST) for the trapping effect, estimated around 170 K, and stability of photo-induced metastable state with a T(LIESST) of 110 K for a complex which is completely low spin until 440 K

Effect of ligand substitution in [Fe(H-trz)2(trz)]BF4 spin crossover nanoparticles

Spin crossover iron(II) 1,2,4-triazole-based coordination compounds in the form of nanoparticles were prepared using a reverse microemulsion technique. Ligand substitution approach was applied to decrease the spin crossover temperature towards room temperature in the well-known [Fe(Htrz)2(trz)]BF4 complex. The compositions of the particles were determined by elemental analysis and thermogravimetry. The morphology was monitored by transition electron microscopy (TEM). The effect associated with the ligand substitution was investigated by optical and magnetic measurements. Transition temperature has been reduced by 33 K comparing the unsubstituted sample to that with 5 % substitution

Effects of the association of an opioid with epidural analgesia for labor and delivery

The purpose of the present study was to evaluate the efficacy and safety of the association bupivacaine with sufentanil for labor and delivery analgesia through a continuous epidural blockade, for both mother and the neonate. A randomized double blind prospective clinical trial was performed including sixty nulliparous women at the Maternity of CAISM/UNICAMP. When requesting analgesia, the women were randomly allocated to two groups: BS, receiving 12.5 mg of bupivacaine with adrenaline plus 30 µg of sufentanil and BP, receiving 12.5 mg of bupivacaine with adrenaline plus placebo. The parameters concerning the quality and duration of analgesia, duration of labor, and also possible effects on the neonate were evaluated. The results showed the superiority of the addition of sufentanil regarding the degree of analgesia during the time of action of the first dose of the local anesthetic. There was no increase in the duration of labor after the onset of analgesia when comparing both groups, nor any difference in the route of delivery. Concerning neonate evaluation, there were no differences between the two groups. It is concluded that the association of 30 µg of sufentanil with the first dose of bupivacaine is safe and efficacious. It improved the quality of analgesia, increased its duration, and did not affect the progress of labor and neonatal outcome.O objetivo deste estudo foi avaliar a eficácia e segurança da associação bupivacaína com sufentanil para a analgesia no trabalho de parto e do parto por meio de um bloqueio peridural contínuo. Realizou-se um ensaio clínico duplo-cego, prospectivo e aleatório, incluindo sessenta mulheres nulíparas da Maternidade do CAISM/UNICAMP. No momento da analgesia, as mulheres foram aleatoriamente alocadas em dois grupos: BS, recebendo 12,5 mg de bupivacaína com adrenalina mais 30 µg de sufentanil e BP, recebendo 12,5 mg de bupivacaína com adrenalina mais placebo. Foram avaliados os parâmetros relativos à qualidade e duração da analgesia, duração do trabalho de parto e também possíveis efeitos sobre o recém-nascido. Os resultados mostraram a superioridade da adição do sufentanil sobre o grau de analgesia durante o tempo de ação da primeira dose de anestésico local. Não houve aumento na duração do trabalho de parto depois do início da analgesia quando se compararam ambos os grupos, nem qualquer diferença quanto à via de parto. Não houve também diferenças entre os grupos com relação à avaliação dos recém-nascidos. Conclui-se que a associação de 30 µg de sufentanil à primeira dose de bupivacaína é segura e eficaz, melhorando a qualidade da analgesia, sua duração e não afetando a progressão do trabalho de parto e o resultado neonatal.32533

Bacteriological study of the superficial sediments of Guanabara bay, RJ, Brazil

Trinta amostras de sedimento foram coletadas na Baía de Guanabara em agosto, novembro e dezembro de 2005. Foram analisados matéria orgânica, coliformes totais e fecais, bactéria heterotrófica, atividade respiratória bacteriana, atividade de esterase e do sistema transportador de elétrons. A matéria orgânica no sedimento superficial variou entre 4 e 6%. O maior nível de coliformes totais e fecais foi 1.7 x 10(5) MPN/g e 1.1 x 10³ MPN/g, respectivamente. Bactérias heterótrofas mostraram o maior valor na estação 7 (4.1 x 10(6) CFU/g) e o menor na estação 3 (7 x 10(4) CFU/g) (nordeste da Baía de Guanabara). A enzima esterase mostrou atividade em todos os sedimentos das 30 estações. A atividade do sistema transportador de elétrons variou entre 0.047 miL O2/h/g e 0.366 miL O2/h/g em seis estações. A cadeia microbiana bêntica é anaeróbia. Os processos como fermentação, desnitrificação e sulfato redução são responsáveis pelos ciclos biogeoquímicos no sedimento da Baía de Guanabara. O despejo de esgoto não tratado no Canal do Mangue da Baía de Guanabara tem favorecido o aumento da carga orgânica e a manutenção de coliformes totais e fecais no sedimento. Os coliformes fecais são bons indicadores de poluição e contaminação orgânica na coluna de água, mas os coliformes totais também poderão ser um grupo candidato para testes de qualidade de sedimento.Thirty sediment samples were collected in Guanabara Bay in August, November and December 2005. The material was analyzed for organic matter, total and faecal coliforms, heterotrophic bacteria, bacterial respiratory activity, esterase activity and electron transport system activity. The organic matter in the superficial sediments (2 cm) ranged from 4 to 6%. The highest level of total coliforms and faecal coliforms were 1.7 x 10(5) MPN/g and 1.1 x 10³ MPN/g, respectively. Heterotrophic bacteria presented the highest values at station 7 (4.1 x 10(6) CFU/g) and the lowest values at station 3 (7 x 10(4) CFU/g) (northwestern part of Guanabara Bay). Esterase enzyme activity showed activity in the sediment of all 30 stations. Electron transport system activity ranged between 0.047 muL O2/h/g and 0.366 muL O2/h/g at six stations. The benthic microbial foodweb is anaerobic. Anaerobic processes such as fermentation, denitrification and sulphate-reduction are responsible for the biogeochemical cycles in the sediment of Guanabara Bay. The input of untreated sewage in the Mangue Channel outflow in Guanabara Bay has favored the increase of the organic load, and the maintenance of the total coliforms and faecal coliforms in the sediment. Faecal coliforms have been reported to be a good indicator of aquatic pollution and organic contamination in the water column, but total coliforms may be an ideal candidate group for sediment quality tests as well

Population overlap and habitat segregation in wintering Black-tailed Godwits Limosa limosa

Distinct breeding populations of migratory species may overlap both spatially and temporally, but differ in patterns of habitat use. This has important implications for population monitoring and conservation. To quantify the extent to which two distinct breeding populations of a migratory shorebird, the Black-tailed Godwit Limosa limosa, overlap spatially, temporally and in their use of different habitats during winter. We use mid-winter counts between 1990 and 2001 to identify the most important sites in Iberia for Black-tailed Godwits. Monthly surveys of estuarine mudflats and rice-fields at one major site, the Tejo estuary in Portugal in 2005-2007, together with detailed tracking of colour-ringed individuals, are used to explore patterns of habitat use and segregation of the Icelandic subspecies L. l. islandica and the nominate continental subspecies L. l. limosa. In the period 1990-2001, over 66 000 Black-tailed Godwits were counted on average in Iberia during mid-winter (January), of which 80% occurred at just four sites: Tejo and Sado lower basins in Portugal, and Coto Dontildeana and Ebro Delta in Spain. Icelandic Black-tailed Godwits are present throughout the winter and forage primarily in estuarine habitats. Continental Black-tailed Godwits are present from December to March and primarily use rice-fields. Iberia supports about 30% of the Icelandic population in winter and most of the continental population during spring passage. While the Icelandic population is currently increasing, the continental population is declining rapidly. Although the estuarine habitats used by Icelandic godwits are largely protected as Natura 2000 sites, the habitat segregation means that conservation actions for the decreasing numbers of continental godwits should focus on protection of rice-fields and re-establishment of freshwater wetlands

Differences Between Intact and Ovariectomized Hemiparkinsonian Rats in Response to L-DOPA, Melatonin, and L-DOPA/Melatonin Coadministration on Motor Behavior and Cytological Alterations

Parkinson?s disease (PD) higher incidence has been observed in postmenopausal women compared to premenopausal women, suggesting estrogen neuroprotective effect. L-DOPA (LD) chronic treatment causes dyskinesia; evidences indicate that LD increases the preexisting oxidative stress condition. This study determines melatonin ability, alone or in combination with LD (LD/Mel) to protect dopaminergic loss induced by 6-OHDA in a rat PD model in ovariectomized (OVX) and intact (with ovaries (W/OV)) rats on motor behavior and cytological alterations, comparing with LD-only treated rats. LD/Mel-treated rats showed dyskinesia decrease (score 5–7.5) and had the best performance in the staircase test (five pellets) throughout all studies. The beam walking time was 20–35 s, showing good coordination (as control group (20–38 s)), dopaminergic cells increase of 22.8% (W/OV rats) and 27.2% (OVX rats) in the contralateral side as well as 100% conservation in the contralateral dendritic spines. Our results suggest that LD/Mel co-administration and estrogen presence result in an efficient treatment to reduce dyskinesia through the conservation of some dopaminergic cells, which imply a well-preserved neuropil of a less denervated striatum. We assume that these results are because of a synergistic effect between LD, melatonin and estrogens

Manganese Inhalation Induces Dopaminergic Cell Loss: Relevance to Parkinson’s Disease

Parkinson’s disease (PD) experimental models are crucial in the assessment of possible therapies. Nevertheless, even though PD was one of the first neurodegenerative conditions to be modeled, there are limitations such as spontaneous recovery; lack of bilateral damage, which is a PD characteristic; animal intensive care after neurotoxin administration; and ultrastructural and biochemical nonspecific alterations but mostly the neurodegenerative time course observed in humans. In this chapter, we investigated the effects of divalent and trivalent manganese inhalation on rats and mice to obtain a novel PD animal model inducing bilateral and progressive dopaminergic cell death. We found that after 5 or 6 months of inhalation, there was more than 70% decrease in the number of TH-immunopositive neurons, and these alterations are correlated with an evident motor performance deficits manifested as akinesia, postural instability, and action tremor. More interesting is the fact that these alterations were reverted with l-DOPA treatment, implying that the motor alterations are associated with nigrostriatal dopaminergic innervation, postulating new light for the understanding of manganese neurotoxicity as an appropriate PD experimental model. Our results are contributing to the development of a suitable PD animal model, reproducible, sensitive, time-efficient, and readily applicable behavioral tests

Malaria in pregnant women living in areas of low transmission on the southeast Brazilian Coast: molecular diagnosis and humoural immunity profile

Key words: autochthonous malaria -pregnancy -molecular diagnostic techniques -humoural -immunity -asymptomatic infections Pregnant women and children are the main groups at risk of acquiring malaria worldwide. Every year, 125 million women from endemic countries become pregnant. In areas of low transmission for Plasmodium falciparum, pregnant women have little or no immunity against the disease and usually suffer severe episodes of malaria. In areas of high or moderate transmission, there are significant levels of acquired immunity and the effects on the mother and foetus are less severe. Although malaria caused by P. falciparum in pregnant women has been widely investigated, the interaction of this cohort with Plasmodium vivax and Plasmodium malariae requires a more comprehensive approach. The World Health Organization (WHO) recommends four antenatal care visits, including malaria tests. However, this criterion depends on the local conditions and specific orientations for each are

The efficacy of suppressive antibiotic treatment in patients managed non-operatively for periprosthetic joint infection and a draining sinus

Objectives: Patients with prosthetic joint infections (PJIs) not suitable for curative surgery may benefit from suppressive antibiotic therapy (SAT). However, the usefulness of SAT in cases with a draining sinus has never been investigated. Methods: A multicentre, retrospective observational cohort study was performed in which patients with a PJI and a sinus tract were eligible for inclusion if managed conservatively and if sufficient follow-up data were available (i.e. at least 2 years). SAT was defined as a period of > 6 months of oral antibiotic therapy. Results: SAT was initiated in 63 of 72 (87.5 %) included patients. Implant retention during follow-up was the same in patients receiving SAT vs. no SAT (79.4 % vs. 88.9 %; pCombining double low line0.68). In total, 27 % of patients using SAT experienced side effects. In addition, the occurrence of prosthetic loosening in initially fixed implants, the need for surgical debridement, or the occurrence of bacteremia during follow-up could not be fully prevented with the use of SAT, which still occurred in 42 %, 6.3 %, and 3.2 % of cases, respectively. However, the sinus tract tended to close more often (42 % vs. 13 %; pCombining double low line0.14), and a higher resolution of pain was observed (35 % vs. 14 %; pCombining double low line0.22) in patients receiving SAT. Conclusions: SAT is not able to fully prevent complications in patients with a draining sinus. However, it may be beneficial in a subset of patients, particularly in those with pain or the hindrance of a draining sinus. A future prospective study, including a higher number of patients not receiving SAT, is needed