Nuevos precursores Al-X-Mo/W (X = Al, Co, V) vía síntesis reticular: Caracterización por 27Al NMR y Raman Microprobe. Aplicación en desulfurización oxidativa (ODS)

Se investigó la actividad de nuevos precursores trimetálicos obtenidos por síntesis reticular, en dos diferentes reacciones de desulfurización oxidativa (ODS): difenilsulfuro a difenilsulfona en presencia de H2O2 y de dibenzotiofeno DBTs mediante terbutilhidroperóxido (t-BuOOH). Se prepararon diversas fases de fórmula general A113-[XMo6] (X= Al (III), Co(III), V(V) y Al13-P[WO4]n combinando el isopolication Keggin [AlO4Al12(OH)24(H2O)12]7+ (Al13) e iso ó heteropolimetalatos del tipo: [XMo6O24H6]3-; [Co2Mo10H4]6-; [WO4]n , [PW9O34]9-, [V2W4]6-. La caracterización se llevó a cabo por XRD, 27Al NMR, FTIR y Raman Microprobe. La estabilidad térmica se estudió por TGA-DTA. Los tests catalíticos se realizaron en batch entre 75 y 80 °C. Los resultados preliminares indican que la actividad ODS aumenta con la densidad electrónica del sustrato, siendo mayor para difenilsulfuro que para DBT. Los catalizadores a base de heteropolimolibdatos presentan una mejor performance en ambas reacciones, mientras el heteroátomo parece mejorar la polarización del enlace Mo-O2t. Catalizadores a base de iso y politungstatos no mostraron actividad excepto aquel conteniendo P como heteroátomo. Asimismo se comprobó por Raman Microprobe, que las fases empleadas conservan su estructura después de la reacción, mostrando la interesante posibilidad de reutilización

Mucosal transmissibility, disease induction and coreceptor switching of R5 SHIVSF162P3N molecular clones in rhesus macaques

Background: Mucosally transmissible and pathogenic CCR5 (R5)-tropic simian-human immunodeficiency virus (SHIV) molecular clones are useful reagents to identity neutralization escape in HIV-1 vaccine experiments and to study the envelope evolutionary process and mechanistic basis for coreceptor switch during the course of natural infection. Results: We observed progression to AIDS in rhesus macaques infected intrarectally with molecular clones of the pathogenic R5 SHIVSF162P3N isolate. Expansion to CXCR4 usage was documented in one diseased macaque that mounted a neutralizing antibody response and in another that failed to do so, with the latter displaying a rapid progressor phenotype. V3 loop envelop glycoprotein gp120 sequence changes that are predictive of a CXCR4 (X4)-using phenotype in HIV-1 subtype B primary isolates, specifically basic amino acid substations at positions 11 (S11R), 24 (G24R) and 25 (D25K) of the loop were detected in the two infected macaques. Functional assays showed that envelopes with V3 S11R or D25K mutation were dual-tropic, infecting CD4+ target cells that expressed either the CCR5 or CXCR4 coreceptor. And, consistent with findings of coreceptor switching in macaques infected with the pathogenic isolate, CXCR4-using variant was first detected in the lymph node of the chronically infected rhesus monkey several weeks prior to its presence in peripheral blood. Moreover, X4 emergence in this macaque coincided with persistent peripheral CD4+ T cell loss and a decline in neutralizing antibody titer that are suggestive of immune deterioration, with macrophages as the major virus-producing cells at the end-stage of disease. Conclusions: The data showed that molecular clones derived from the R5 SHIVSF162P3N isolate are mucosally transmissible and induced disease in a manner similar to that observed in HIV-1 infected individuals, providing a relevant and useful animal infection model for in-depth analyses of host selection pressures and the env evolutionary changes that influence disease outcome, coreceptor switching and vaccine escape

Improvement of HDS catalysts through the modification of the oxidic precursor with 1,5-pentanediol: Gas phase sulfidation and thiophene conversion

AbstractThe performance, in thiophene HDS, of a CoMo/Al2O3 catalyst was successfully improved through chemical modification of its oxidic precursor by impregnation with 1,5-pentanediol solution. The gas phase activation with a H2/H2S mixture was followed by thermogravimetric analysis coupled with a rapid chromatograph; the catalysts were characterized at different steps of the activation using X-ray photoelectron spectroscopy (XPS). It appeared that the addition of the organic agent retards the sulfidation of the supported metals, leading to a simultaneous sulfidation of Co and Mo atoms. This induces the formation of smaller MoS2 slabs and thus an increase in the number of active CoMoS sites, directly correlated with the better HDS performance of the modified solid. The role of 1,5-pentanediol is likely to inhibit, at low temperature, the adsorption of H2S on the solid and thus the sulfidation of the supported metals

Being Pathogenic, Plastic, and Sexual while Living with a Nearly Minimal Bacterial Genome

Mycoplasmas are commonly described as the simplest self-replicating organisms, whose evolution was mainly characterized by genome downsizing with a proposed evolutionary scenario similar to that of obligate intracellular bacteria such as insect endosymbionts. Thus far, analysis of mycoplasma genomes indicates a low level of horizontal gene transfer (HGT) implying that DNA acquisition is strongly limited in these minimal bacteria. In this study, the genome of the ruminant pathogen Mycoplasma agalactiae was sequenced. Comparative genomic data and phylogenetic tree reconstruction revealed that ∼18% of its small genome (877,438 bp) has undergone HGT with the phylogenetically distinct mycoides cluster, which is composed of significant ruminant pathogens. HGT involves genes often found as clusters, several of which encode lipoproteins that usually play an important role in mycoplasma–host interaction. A decayed form of a conjugative element also described in a member of the mycoides cluster was found in the M. agalactiae genome, suggesting that HGT may have occurred by mobilizing a related genetic element. The possibility of HGT events among other mycoplasmas was evaluated with the available sequenced genomes. Our data indicate marginal levels of HGT among Mycoplasma species except for those described above and, to a lesser extent, for those observed in between the two bird pathogens, M. gallisepticum and M. synoviae. This first description of large-scale HGT among mycoplasmas sharing the same ecological niche challenges the generally accepted evolutionary scenario in which gene loss is the main driving force of mycoplasma evolution. The latter clearly differs from that of other bacteria with small genomes, particularly obligate intracellular bacteria that are isolated within host cells. Consequently, mycoplasmas are not only able to subvert complex hosts but presumably have retained sexual competence, a trait that may prevent them from genome stasis and contribute to adaptation to new hosts

Pharmaceuticals released from senior residences: occurrence and risk evaluation

One of the main pursuits, yet most difficult, in monitoring studies is to identify the sources of environmental pollution. In this study, we have identified health-care facilities from south European countries as an important source of pharmaceuticals in the environment. We have estimated that compounds consumed in by the elderly and released from effluents of senior residences can reach river waters at a concentration higher than 0.01 μg/L, which is the European Medicines Agency (EMA) threshold for risk evaluation of pharmaceuticals in surface waters. This study has been based on five health institutions in Portugal, Spain, and France, with 52 to 130 beds. We have compiled the pharmaceuticals dispensed on a daily base and calculated the consumption rates. From 54.9 to 1801 g of pharmaceuticals are consumed daily, with laxatives, analgesics, antiepileptics, antibiotics, and antidiabetic agents being the main drug families administered. According to excretion rates, dilution in the sewerage system, and elimination in wastewater treatment plants, macrogol, metformin, paracetamol, acetylcysteine, amoxicillin, and gabapentin, among others, are expected to reach river waters. Finally, we discuss the risk management actions related to the discharge of pharmaceuticals from senior residences to surface waters

Removal of a subset of non-essential genes fully attenuates a highly virulent mycoplasma strain

Mycoplasmas are the smallest free-living organisms and cause a number of economically important diseases affecting humans, animals, insects, and plants. Here, we demonstrate that highly virulent Mycoplasma mycoides subspecies capri (Mmc) can be fully attenuated via targeted deletion of non-essential genes encoding, among others, potential virulence traits. Five genomic regions, representing approximately 10% of the original Mmc genome, were successively deleted using Saccharomyces cerevisiae as an engineering platform. Specifically, a total of 68 genes out of the 432 genes verified to be individually non-essential in the JCVI-Syn3.0 minimal cell, were excised from the genome. In vitro characterization showed that this mutant was similar to its parental strain in terms of its doubling time, even though 10% of the genome content were removed. A novel in vivo challenge model in goats revealed that the wild-type parental strain caused marked necrotizing inflammation at the site of inoculation, septicemia and all animals reached endpoint criteria within 6 days after experimental infection. This is in contrast to the mutant strain, which caused no clinical signs nor pathomorphological lesions. These results highlight, for the first time, the rational design, construction and complete attenuation of a Mycoplasma strain via synthetic genomics tools. Trait addition using the yeast-based genome engineering platform and subsequent in vitro or in vivo trials employing the Mycoplasma chassis will allow us to dissect the role of individual candidate Mycoplasma virulence factors and lead the way for the development of an attenuated designer vaccine

The ubiquitous cross-coupling catalyst system ‘Pd(OAc)2’/2PPh3 forms a unique dinuclear PdI complex: an important entry point into catalytically competent cyclic Pd3 clusters

Palladium(II) acetate ‘Pd(OAc)2’/nPPh3 is a ubiquitous precatalyst system for cross-coupling reactions. It is widely accepted that reduction of in situ generated trans-[Pd(OAc)2(PPh3)2] affords [Pd0(PPh3)n] and/or [Pd0(PPh3)2(OAc)]- species which undergo oxidative addition reactions with organohalides – the first committed step in cross-coupling catalytic cycles. In this paper we report for the first time that reaction of Pd3(OAc)6 with 6 equivalents of PPh3 (i.e. a Pd/PPh3 ratio of 1:2) affords a novel dinuclear PdI complex [Pd2(µ-PPh2)(µ2-OAc)(PPh3)2] as the major product, the elusive species resisting characterization until now. While unstable, the dinuclear PdI complex reacts with CH2Cl2, p-fluoroiodobenzene or 2-bromopyridine to afford Pd3 cluster complexes containing bridging halide ligands, i.e. [Pd3(X)(PPh2)2(PPh3)3]X, carrying an overall 4/3 oxidation state (at Pd). Use of 2-bromopyridine was critical in understanding that a putative 14-electron mononuclear ‘PdII(R)(X)(PPh3)’ is released on forming [Pd3(X)(PPh2)2(PPh3)3]X clusters from [Pd2(µ-PPh2)(µ2-OAc)(PPh3)2]. Altering the Pd/PPh3 ratio to 1:4 forms Pd0(PPh3)3 quantitatively. In an exemplar Suzuki-Miyaura cross-coupling reaction the importance of the ‘Pd(OAc)2’/nPPh3 ratio is demonstrated; catalytic efficacy is significantly enhanced when n = 2. Employing ‘Pd(OAc)2’/PPh3 in a 1:2 ratio leads to the generation of [Pd2(µ-PPh2)(µ2-OAc)(PPh3)2] which upon reaction with organohalides (i.e. substrate) forms a reactive Pd3 clusters species. These higher nuclearity species are the cross-coupling catalyst species, when employing a ‘Pd(OAc)2’/PPh3 of 1:2, for which there are profound implications for understanding downstream product selectivities, chemo-, regio- and stereoselectivities

What can inactivity (in its various forms) reveal about affective states in non-human animals? A review

Captive/domestic animals are often described as inactive, with the implicit or explicit implication that this high level of inactivity is a welfare problem. Conversely, not being inactive enough may also indicate or cause poor welfare. In humans, too much inactivity can certainly be associated with either negative or positive affective states. In non-human animals, however, the affective states associated with elevated or suppressed levels of inactivity are still not well understood. Part of the complexity is due to the fact that there are many different forms of inactivity, each likely associated with very different affective states. This paper has two aims. One is to identify specific forms of inactivity that can be used as indicators of specific affective states in animals. The other is to identify issues that need to be resolved before we could validly use the remaining, not yet validated forms of inactivity as indicators of affective state. We briefly discuss how inactivity is defined and assessed in the literature, and then how inactivity in its various forms relates to affective (either negative or positive) states in animals, basing our reasoning on linguistic reports of affective states collected from humans displaying inactivity phenotypically similar to that displayed by animals in similar situations, and, when possible, on pharmacological validation. Specific forms of inactivity expressed in response to perceived threats (freezing, tonic immobility, and hiding) appear to be, to date, the best-validated indicators of specific affective states in animals. We also identify a number of specific forms of inactivity likely to reflect either negative (associated with ill-heath, boredom-like, and depression-like conditions), or positive states (e.g. ‘sun-basking’, post-consummatory inactivity), although further research is warranted before we could use those forms as indicators of the affective states. We further discuss the relationship between increased inactivity and affective states by presenting misleading situations likely to yield wrong conclusions. We conclude that more attention should be paid to inactivity in animal welfare studies: specific forms of inactivity identified in this paper are, or have the potential to be, useful indicators of affective (welfare) states in animals

Contribution à la lutte contre la Péripneumonie contagieuse bovine (typage moléculaire par MLVA et inactivation de gènes chez Mycoplasma mycoides subsp. mycoides Small Colony)

Mycoplasma mycoides subsp. mycoides Small Colony (MmmSC) est l'agent infectieux responsable de la péripneumonie contagieuse bovine (PPCB), une maladie causant des pertes majeures dans les élevages bovins. Alors que le risque de réemergence de cette maladie en Europe est une réalité, celle-ci reste à l'état endémique dans toute la région sub-saharienne de l'Afrique. La compréhension des modes de dissémination de la PPCB est essentielle pour contrôler la maladie. Les outils de typage, ne cessaires au suivi des épidémies, sont pour l'instant insuffisants pour différencier précisément les souches de MmmSC, notamment celles d'origine européenne. Nous avons développé une méthode de typage moléculaire basée sur l'étude de minisatellites polymorphes (MLVA ou Multilocus VNTR Analysis). Trois minisatellites sélectionnés ont permis de répartir un échantiillonnage de 32 souches en 17 groupes. Les 14 souches européennes testées sont réparties en 5 groupes, ce qui représente une amélioration de la sensibilité par rapport aux techniques existantes. La prophylaxie en Afrique repose principalement sur l'utilisation de souches vaccinales atténuées par passages ex vivo. Ces dernières n'apportent qu'une protection limitée dans le temps et induisent parfois des effets secondaires indésirables. En vue de produire de nouveaux vaccins par inactivation de facteurs de virulence, nous avons mis au point une méthode de mutagenèse par transposition. Des banques de données ont été obtenues et l'insertion du transposon dans les gènes d'intérêt a été démontrée. Un mutant n'exprimant plus la lipoprotéine majeure LppQ a été caractérisé. Enfin, une amélioration du transposon utilisé permet maintenant d'envisager la production de mutants n'hébergeant plus de gènes de résistance aux antibiotiques, ouvrant ainsi la voie à l'élaboration de souches vaccinales atténuées par génie génétique.Mycoplasma mycoides subsp. Small Colony ( MmmSC) is the etiologic agent of Contagious Bovine Pleuropneumoniae (CPP), a disease causing important losses in cattle herds. The threat of a re-emergence of this disease is a reality in Europe and CBPP is still endemic in Africa. Understanding how CBPP spreads during an epidemic is essential to control this disease. However, typing tools are inefficient to discriminate precisely between the different strains of MmmSC, especially European strains. We developed a typing method based upon the study of polymorphic minisatellites (MLVA or MultiLocus VNTR Analysis). Three of the identified minisatellites permitted the distribution of the 32 studied strains into 17 groups, and of the 14 European strains into 5 groups. This latter result represents an improved sensitivity of MmmSC typing compared to existing methods. The CBPP prophylaxis in Africa is mainly based upon vaccination, using MmmSC, strains that were attenuated by several passages ex vivo. The protection they afford is too time-limited and induce sometimes severe post-vaccine reactions. To produce new and safer vaccines by inactivating MmmSC virulence determinants, we developed a transposon-based mutagenesis method. Mutant libraries were obtained and the transposon insertion into genes of interest was demonstrated. A mutant, defective in the lipoprotein LppQ, a major antigen, was isolated and characterized.BORDEAUX2-BU Santé (330632101) / SudocSudocFranceF