The nature of the Cr-C bond: direct estimation of aromaticity in Fischer carbenes

Report for the scientific sojourn at the the Philipps-Universität Marburg, Germany, from september to december 2007. For the first, we employed the Energy-Decomposition Analysis (EDA) to investigate aromaticity on Fischer carbenes as it is related through all the reaction mechanisms studied in my PhD thesis. This powerful tool, compared with other well-known aromaticity indices in the literature like NICS, is useful not only for quantitative results but also to measure the degree of conjugation or hyperconjugation in molecules. Our results showed for the annelated benzenoid systems studied here, that electron density is more concentrated on the outer rings than in the central one. The strain-induced bond localization plays a major role as a driven force to keep the more substituted ring as the less aromatic. The discussion presented in this work was contrasted at different levels of theory to calibrate the method and ensure the consistency of our results. We think these conclusions can also be extended to arene chemistry for explaining aromaticity and regioselectivity reactions found in those systems.In the second work, we have employed the Turbomole program package and density-functionals of the best performance in the state of art, to explore reaction mechanisms in the noble gas chemistry. Particularly, we were interested in compounds of the form H--Ng--Ng--F (where Ng (Noble Gas) = Ar, Kr and Xe) and we investigated the relative stability of these species. Our quantum chemical calculations predict that the dixenon compound HXeXeF has an activation barrier for decomposition of 11 kcal/mol which should be large enough to identify the molecule in a low-temperature matrix. The other noble gases present lower activation barriers and therefore are more labile and difficult to be observable systems experimentally.

Fibrogenesis and collagen resorption in the heart and skeletal muscle of Calomys callosus experimentally infected with Trypanosoma cruzi: immunohistochemical identification of extracellular matrix components

Intense inflammatory lesions and early development of interstitial fibrosis of the myocardium and skeletal muscle with spontaneous regression, have been described in Calomys callosus infected with Trypanosoma cruzi. The genetic types of collagen present in this model were investigated through immunohistochemistry using specific antibodies, combined with histopathology and Picro-Sirius staining of collagen. Thirty-five calomys were infected with the Colombian strain of T. cruzi and sacrificed at 24, 30, 40, 60 and 90 days post-infection. Inflammatory lesions and fibrogenesis were prominent at the early phase of infection and significantly decreased during late infection. Immunoisotyping of the matrix components was performed by indirect immunofluorescence on 5 µm thick cryostat sections using specific antibodies against laminin, fibronectin and isotypes I, III and IV of collagen. In the early phase, positive deposits of all the matrix components were present, with predominance of fibronectin, laminin and collagens types I and III in the myocardium and of types III and IV in the skeletal muscles. From the 40th day, type IV collagen predominates in the heart. At the late phase of infection (60th to 90th day), a clear fragmentation and decrease of all the matrix components were detected. Findings of the present study indicate that a modulation of the inflammatory process occurs in the model of C. callosus, leading to spontaneous regression of fibrosis independent of the genetic types of collagen involved in this process.

Analyse UBM du site de filtration après sclérectomie profonde postérieure modifiée utillisant un tube Ex-PRESS? X-50

Purpose: To study the filtering site using ultrasound biomicroscopy. (UBM) after posterior deep sclerectomy with Ex-PRESS? X-50 implant in patients undergoing filtering surgery.¦Methods: Twenty-six patients that participated in this prospective, non comparative study underwent a posterior deep sclerectomy and an Ex- PRESS? X-50 tube implantation. Clinical outcome factors recorded include: intraocular pressure, number of antiglaucoma medications, best corrected visual acuity (BCVA), frequency and types of complications. Six months postoperatively, an ultrasound biomicroscopy examination was performed.¦Results: Mean follow up was 12.0±3.4 months. Mean IOP decreased from 21 ±5.7 mmHg to 12.4±3 mmHg. At last follow-up examination, 65% of eyes had a complete success and 30% a qualified success. The mean number of antiglaucoma medications decreased from 2.5±1.2 preoperatively to 0.7±1 at the last follow-up postoperatively. BCVA was not changed. 27 complications were observed. On the UBM images, the mean intrascleral space volume was 0.25±0.27 mm3 and no relationship was found between volume and intraocular pressure reduction. We noted in 5/26 (19%) eyes a suprachoroïdal hypoechoic. Low-reflective blebs (L-type) were the most common: 15/26 (58%). No correlation between UBM findings and surgical success was evident.¦Conclusions: Deep sclerectomy with Ex-PRESS? X-50 tube implantation seems an efficient glaucoma surgery. It allows satisfactory IOP reduction with a low number of post operative complications. The advantages of deep sclerectomy with collagen implant are maintained with this modified technique. In both, the same reflective types of filtering blebs are present (high, low, encapsulated and flat). The UBM underlines the three mechanisms of aqueous humor resorption previously identified but no correlation with surgical success can be proved.¦-¦Ce travail de thèse est une analyse par ultrasonographic biomicroscopique (UBM) du site de filtration après sclérectomie profonde postérieure modifiée avec implantation d'un tube Ex- PRESS? X-50.¦Vingt six patients atteints d'un glaucome à angle ouvert, ont participé à cette étude prospective et non-comparative. Le critère d'inclusion est un glaucome à angle ouvert non contrôlé malgré un traitement topique maximal.¦Différents types de chirurgie filtrante sont effectués dans la chirurgie du glaucome dont la trabéculectomie et la sclérectomie profonde.¦L'intervention chirurgicale pratiquée dans cette étude consiste en l'implantation d'un tube Ex-PRESS? X-50 de format défini (3 mm de longueur et 50 μπι de diamètre interne) dans la chambre antérieure,au niveau du trabeculum, sous un volet scléral, ce qui permet le drainage de l'humeur aqueuse vers les espaces sous-conjonctivaux, avec diminution de la pression intraoculaire.¦Cette technique implique uniquement une dissection d'un volet scléral superficiel , sans volet scléral profond comme d'une sclérectomie profonde classique.¦Les modes de fonctionnement de cette sclérectomie profonde modifiée sont explorés par UBM, qui donne des images à haute résolution, semblables à des coupes anatomiques. Le volume de l'espace intrascléral créé artificiellement peut en effet être mesuré et mis en corrélation avec la pression intraoculaire et donc avec le taux de succès. Les différents types d'échogénécité de la bulle de filtration sous-conjonctivale provoquée par la dérivation de l'humeur aqueuse sont également observés. La présence éventuelle d'une filtration supplémentaire au niveau choroïdien est aussi détectée.¦De février 2007 à juin 2008, nous avons suivi chez les vingt six yeux des vingt six patients le volume intrascléral, la filtration sous-conjonctivale et la filtration choroïdienne le cas échéant, de même que l'acuité visuelle, la pression intraoculaire, le nombre de traitement antihypertenseur topique et les complications.¦Les résultats démontrent une réduction de 41 % par rapport à la pression intraoculaire préopératoire, ce qui est statistiquement significatif (p<0.0005). En ce qui concerne l'acuité visuelle, les valeurs demeurent stables. Par ailleurs, le nombre de médicaments antiglaucomateux diminue de façon significative de 2.5 ± 1.2 en préopératoire à 0.7 ± 1.0 au dernier examen (p<0.0005). Le volume de l'espace intrascléral, apparaissant toujours en échographie d'aspect fusiforme, n'est pas corrélé de façon significative avec un meilleur succès chirurgical bien que l'on aperçoive une tendance à une corrélation entre un plus grand volume et une pression intraoculaire plus basse.¦La classification la bulle de filtration se fait selon les 4 catégories de bulle de filtration décrites dans la littérature. La répartition révèle une majorité de type L soit hypoéchogène: 15/26 (58%) et une proportion identique, soit, 4/26 (16%), de bulles hyperéchogènes (type H) et encapsulées (type E); les bulles de filtration plates et hyperéchogènes (type F) sont les moins nombreuses 3/26 (11 %).¦La ligne hyporéflective visible dans 19 % des cas entre la sclère et la choroïde représentant potentiellement un drainage suprachoroïdien, n'est pas associée statistiquement à une meilleure filtration et une pression intraoculaire plus basse mais demeure une troisième voie de filtration, en plus de la filtration sous-conjonctivale et intrasclérale.¦En conclusion, cette technique différente, offrant une plus grande sécurité et des résultats satisfaisants sur l'abaissement de la pression intraoculaire, peut être, dans certains cas, une alternative à la sclérectomie profonde classique ,dont elle partage les mécanismes de filtration objectivés par ultrasonographic biomicrioscopique.

An image quality comparison of standard and dual-side read CR systems for pediatric radiology.

An objective analysis of image quality parameters was performed for a computed radiography (CR) system using both standard single-side and prototype dual-side read plates. The pre-sampled modulation transfer function (MTF), noise power spectrum (NPS), and detective quantum efficiency (DQE) for the systems were determined at three different beam qualities representative of pediatric chest radiography, at an entrance detector air kerma of 5 microGy. The NPS and DQE measurements were realized under clinically relevant x-ray spectra for pediatric radiology, including x-ray scatter radiations. Compared to the standard single-side read system, the MTF for the dual-side read system is reduced, but this is offset by a significant decrease in image noise, resulting in a marked increase in DQE (+40%) in the low spatial frequency range. Thus, for the same image quality, the new technology permits the CR system to be used at a reduced dose level.

Evaluation of RbCl and CrCl3 as markers of Triatoma brasiliensis (Hemiptera: Reduviidae) nymphs: persistence and influence of Rb and Cr on triatomine biology

In order to mark Triatoma brasiliensis, the vector of Chagas disease in Brazil, two chemical compounds, rubidium chloride (RbCl) and chromium chloride (CrCl3), were tested. First, 199 N2-N5 nymphs were fed on blood with 0.025M RbCl. Rb marker positivity ranged from 2.5% (N3)-70% (N2), with a maximum persistence of 98 days. Second, 265 N2-N5 nymphs were fed on blood containing 0.0015M CrCl3. Cr marker positivity ranged up to 93% (N5), with a maximum persistence of 119 days. Finally, we blood fed 213 T. brasiliensis to investigate whether CrCl3 altered the biology of this insect. The developmental time of T. brasiliensis was unaltered, but the survival of the Cr-marked group was lower than that of the control group. Differences in the mean fecundity of the control (mean of 156.1) and experimental (mean of 135.6) groups were not statistically significant and 100% of the egg batches of females Cr-marked as nymphs were positive. In conclusion, CrCl3 is a useful tool for marking T. brasiliensis nymphs due to its high positivity and persistence.

The first report of the qnrB19, qnrS1 and aac(6´)-Ib-cr genes in urinary isolates of ciprofloxacin-resistant Escherichia coli in Brazil

In this study, we investigated the presence of plasmid-mediated quinolone resistance (PMQR) genes among 101 ciprofloxacin-resistant urinary Escherichia coli isolates and searched for mutations in the quinolone-resistance-determining regions (QRDRs) of the DNA gyrase and topoisomerase IV genes in PMQR-carrying isolates. Eight isolates harboured the qnr and aac(6')-Ib-cr genes (3 qnrS1, 1 qnrB19 and 4 aac(6')-Ib-cr). A mutational analysis of the QRDRs in qnr and aac(6')-Ib-cr-positive isolates revealed mutations in gyrA, parC and parE that might be associated with high levels of resistance to quinolones. No mutation was detected in gyrB. Rare gyrA, parC and parE mutations were detected outside of the QRDRs. This is the first report of qnrB19, qnrS1 and aac(6')-Ib-cr -carrying E. coli isolates in Brazil.

Evaluation of three automated systems for susceptibility testing of enterobacteria containing qnrB, qnrS, and/or aac(6')-Ib-cr.

The accuracy of the MicroScan WalkAway, BD Phoenix, and Vitek-2 systems for susceptibility testing of quinolones and aminoglycosides against 68 enterobacteria containing qnrB, qnrS, and/or aac(6 ')-Ib-cr was evaluated using reference microdilution. Overall, one very major error (0.09%), 6 major errors (0.52%), and 45 minor errors (3.89%) were noted.

Diets based on virgin olive oil or fish oil but not on sunflower oil prevent age-related alveolar bone resorption by mitochondrial-related mechanisms.

BACKGROUND/OBJECTIVES Aging enhances frequency of chronic diseases like cardiovascular diseases or periodontitis. Here we reproduced an age-dependent model of the periodontium, a fully physiological approach to periodontal conditions, to evaluate the impact of dietary fat type on gingival tissue of young (6 months old) and old (24 months old) rats. METHODS/FINDINGS Animals were fed life-long on diets based on monounsaturated fatty acids (MUFA) as virgin olive oil, n-6 polyunsaturated fatty acids (n-6PUFA), as sunflower oil, or n-3PUFA, as fish oil. Age-related alveolar bone loss was higher in n-6PUFA fed rats, probably as a consequence of the ablation of the cell capacity to adapt to aging. Gene expression analysis suggests that MUFA or n-3PUFA allowed mitochondria to maintain an adequate turnover through induction of biogenesis, autophagy and the antioxidant systems, and avoiding mitochondrial electron transport system alterations. CONCLUSIONS The main finding is that the enhanced alveolar bone loss associated to age may be targeted by an appropriate dietary treatment. The mechanisms involved in this phenomenon are related with an ablation of the cell capacity to adapt to aging. Thus, MUFA or n-3PUFA might allow mitochondrial maintaining turnover through biogenesis or autophagy. They might also be able to induce the corresponding antioxidant systems to counteract age-related oxidative stress, and do not inhibit mitochondrial electron transport chain. From the nutritional and clinical point of view, it is noteworthy that the potential treatments to attenuate alveolar bone loss (a feature of periodontal disease) associated to age could be similar to some of the proposed for the prevention and treatment of cardiovascular diseases, a group of pathologies recently associated with age-related periodontitis.

Epiphyseal fracture of distal humerus in children, treated with bio-absorbable materials: one year follow-up

Introduction: The use of bioabsorbable materials for orthopaedic useand traumatic fracture fixation in children has been poorly investigatedin the litterature and the effects on growing bones seem contradictory.The aim of the study is to compare the clinical and radiological resultsand evolution between bioabsorbable and traditional K-Wires for thetreatment of elbow epiphyseal fractures in children.Method: From jan. 2008 to Dec. 2009 21 children with similar fracturesand age were separated in two groups according to the way of fracturefixation: bioabsorbable K-Wire group and traditional K-Wire group.Follow-up was done at 3, 6 and 12 month post-operatively. Range ofmotion and elbow stability were measured for all patients. Theradiological evolution of the two groups were compared in term ofconsolidation, ossous resorption and radiolucencies. The clinicalresults were compared according to the Mayo Elbow Peformancescore. Controlateral elbow is compared with injured elbow in the twogroups.Results: In the bioabsorbable K-wire group, there were 10 children,including 5 girles and 5 boys with an average age of 9.5 years, rangingfrom 5 to 14 years. They were 7 external condylar fractures and3 epitrochlear fractures. In the traditional K-Wire group there were11 children, 2 girls and 9 boys with an average age of 7.6 years,ranging from 4 to 14 years. There were 10 external condylar fracturesand 1 epitrochlear fracture. At first follow up. The Mayo ElbowPerformance score was 93.8 (85-100 )for the bioabsorbable K-Wiregroup and 95.5 (85-100) for the traditional K-Wire group. In twochildren from the bioabsorbable K-Wire group there were transitoryradiolucencies along the wire tract on the x-ray, without clinicalmanifestation of it.We didn't see any premature closure of growingcartilage.Discussion: There is no significant differencies in term of clinical andradiological outcome between the two groups. The use ofbioabsorbable pins seems to be a good alternative to removabletraditional materials, avoiding a second operation.

Kuranishi type Moduli Spaces for proper CR submersions fibering over the circle

Kuranishi's fundamental result (1962) associates to any compact complex manifold X&sub&0&/sub& a finite-dimensional analytic space which has to be thought of as a local moduli space of complex structures close to X&sub&0&/sub&. In this paper, we give an analogous statement for Levi-flat CR manifolds fibering properly over the circle by describing explicitely an infinite-dimensional Kuranishi type local moduli space of Levi-flat CR structures. We interpret this result in terms of Kodaira-Spencer deformation theory making clear the likenesses as well as the differences with the classical case. The article ends with applications and examples.

Variétés CR polarisées et G-polarisées, partie I

Polarized and G-polarized CR manifolds are smooth manifolds endowed with a double structure: a real foliation &em&F&/em& (given by the action of a Lie group G in the G-polarized case) and a transverse CR distribution. Polarized means that (E,J) is roughly speaking invariant by&em&F&/em&. Both structures are therefore linked up. The interplay between them gives to polarized CR-manifolds a very rich geometry. In this paper, we study the properties of polarized and G-polarized manifolds, putting special emphasis on their deformations.

[Félix] Léonard [portrait du boxeur français, salle Cré] : [photographie de presse] / [Agence Rol]

Référence bibliographique : Rol, 57120

M. Cré [dans la salle de boxe portant son nom, 56 rue Rodier, à Paris] : [photographie de presse] / [Agence Rol]

Référence bibliographique : Rol, 57118

Walter Ross [boxeur anglais, s'entraînant salle Cré, rue Rodier, à Paris] : [photographie de presse] / [Agence Rol]

Référence bibliographique : Rol, 57121

Dumas [portrait du boxeur, salle Cré] : [photographie de presse] / [Agence Rol]

Référence bibliographique : Rol, 57119