Characteristics and management of Enterobacteriaceae harboring IMP-4 or IMP-8 carbapenemase in a tertiary hospital.

Background: The emergence of Enterobacteriaceae harboring IMP-4 or IMP-8 carbapenemases is rare. We report an occurrence of Enterobacteriaceae harboring IMP-4 or IMP-8 carbapenemases in a Chinese tertiary care hospital from November 2010 to December 2012. Methods: The clinical characteristics of 30 patients were described. The genetic relationship of isolates was determined by pulsed-field gel electrophoresis (PFGE). Carbapenemases were detected by modified Hodge test (MHT) and polymerase chain reactions (PCRs). Amplicons were sequenced and blasted to determine the genotype. Results: Most infected patients were from intensive care unit and had complex and serious underlying illnesses requiring mechanical ventilation. PFGE revealed that Klebsiella pneumoniae showed two major PFGE types. Two Klebsiella oxytoca had an indistinguishable PFGE pattern, while four Enterobacter cloacae were different strains. The sequencing studies showed Enterobacteriaceae harboring IMP-4 or IMP-8 carbapenemase in the 23 infected patients. The majority of patients had infections with the carbapenemase-producing Enterobacteriaceae (CPE) strain, most were successfully treated with a range of antibiotics and discharged. Conclusion: It is important to maintain a high index of suspicion to screen for carbapenemase-producing Enterobacteriaceae strains. Rapid identification of these strains and implementation of stringent procedures are the key to prevent major outbreaks in a hospital setting. Keywords:

Experiences of health professionals with nutritional support of critically ill patients in tertiary hospitals in Malawi

Background Nutritional support is a recognized determinant of outcome in critically ill patients. Development of critical care services in low-income countries has not been accompanied by certain appropriate ancillary services and interventions, such as adequate nutritional support. This study was designed to investigate the experiences of health professionals who have provided nutritional supportive care to critically ill patients admitted to two major central hospitals in Malawi, with the aim of identifying the common practices in nutritional support in these settings. Materials and Methods A cross-sectional study in which 50 health professionals working in intensive care and high dependency units, admitting both adult and pediatric patients, were interviewed using a semi-structured questionnaire. Data were coded and then analyzed using SPSS version 16.0. Responses between the two hospitals were compared using Fisher’s exact test. Results There was no difference in the composition of respondents from the two hospitals. About 60% of respondents had had experience with nutritional supplementation in their patients—mainly enteral. The most commonly used formulations were the “ready-to-use therapeutic feeds,” followed by modified milk. A high percentage of respondents (40%) reported having used dextrose solution as the sole nutritional supplement. Lack of in-service training, nonexistent nutrition protocols pertaining to acutely and critically ill patients, and a lack of clinical nutritionists were the major challenges identified. Conclusion Knowledge of nutrient supplementation was poor among the respondents. The use of ready-to-use therapeutic feeds was quite common, although there is no evidence of its effectiveness in care of acutely critically ill patients. There is a need to establish nutritional support teams in these tertiary hospitals. Clinical nutritionists would ideally help train and play leadership roles in such teams, who would be responsible for assessing patients for their nutritional needs, and ensuring that the feeds provided to patients are appropriate and adequate for their needs.

Preparação e caracterização de filmes cerâmicos para cátodos de células a combustível de óxido sólido

Alternative and clean energy generation research has been intensified in last decades. Among the alternatives, fuel cells are one of the most important. There are different types of fuel cells, among which stands out intermediate temperature solid oxide fuel cell (IT-SOFC) matter of the present work. For application as cathode on this type of devices, the ceramic Ba0.5Sr0.5C0.8Fe0.2O3-δ doped with rare earth ions (Nd, Sm) have been quite promising because they show good ionic conductivity and operate at relatively low temperatures (500 - 800°C). In this work, Ba0.5Sr0.5Co0.8Fe0.2O3-δ, (BaSr)0.5Sm0.5Co0.8Fe0.2O3-δ and (BaSr)0.5Nd0.5C0.8Fe0.2O3-δ were obtained by modified Pechini method, making use of gelatin as polymerizing agent. The powders were characterized by X-Ray Diffraction (XRD), Temperature Programmed Reduction (TPR) and Scanning Electron Microscopy (SEM). The perovskite phase was observed in all X-ray patterns for the materials Ba0.5Sr0.5C0.8Fe0.2O3-δ doped with rare earth ions (Nd, Sm). The SEM images showed that the materials have a characteristics porous, with very uniform pore distribution, which are favorable for application as cathodes. Subsequently, screen-printed assymmetrical cells were studied by impedance spectroscopy, to assess the kinetics of the cathode for the reduction reaction of oxygen. The best resistance to the specific area was found for the cathode BSSCF sintered at 1050 °C for 4 hours with around 0.15 Ω.cm2 at 750 °C as well as cathodes BSNCF and BSCF obtained resistances specific area of 0.2 and 0.73 Ω.cm2, respectively, for the same conditions. The polarization curves showed similar behavior to the best cathodes BSSCF and BSNCF, such combination of properties indicates that the film potentially depict good performance as IT-SOFC cathodes

Flexor Digitorum Superficialis and Flexor Digitorum Profundus with separated sheaths, a new normal variation in human

Case description: A 25 years old man presented with a laceration on radial side of proximal phalanx of 4th finger (zone II flexor) which was due to cut with glass. Clinical findings: The sheaths of Tendons of flexor digitorum sperficialis and profundus were not the same and each tendon had a separate sheath. Treatment and outcome: The tendons were reconstructed by modified Kessler sutures, after 15 months the patient had a 30 degrees of extension lag even after physiotherapy courses. Clinical relevance: This is the first reported of such normal variation in human hand tendon anatomy.

Toxoplasma gondii Infection in Hunted Wild Boars (Sus scrofa): Heart Meat Juice as an Alternative Sample to Serum for the Detection of Antibodies

Toxoplasmosis is a global zoonosis caused by the protozoan parasite Toxoplasma gondii. Detection of antibodies to T. gondii in serum samples from hunted animals may represent a key step for public health protection. It is also important to assess the circulation of this parasite in wild boar population. However, in hunted animals, collection of blood is not feasible and meat juice may represent an alternative sample. The purpose of the present study was to evaluate heart meat juice of hunted wild boars as an alternative sample for post-mortem detection of antibodies to T. gondii by modified agglutination test (MAT). The agreement beyond chance between results from meat juice assessed with Cohen’s kappa coefficient revealed that the 1:20 meat juice dilution provided the highest agreement. McNemars’s test further revealed 1:10 as the most suitable meat juice dilution, as the proportion of positive paired samples (serum and meat juice from the same animal) did not differ at this dilution. All together, these results suggest a reasonable accuracy of heart meat juice to detect antibodies to T. gondii by MAT and support it as an alternative sample in post-mortem analysis in hunted wild boars.

Estudio conformacional de péptidos modificados de las proteínas STARP, CelTOS, TRSP y SERA 5 de Plasmodium falciparum y su relación con una respuesta inmune en malaria

El desarrollo de una vacuna contra malaria es un área de exploración activa pero con enormes retos debido especialmente a la complejidad del ciclo del parásito. Así, es necesario bloquear las diferentes etapas de la invasión que tiene el Plasmodium falciparum y extraer de ellas la mayor información posible de la artillería que utiliza para su ataque. Para esto, péptidos de las proteínas STARP, CelTOS y TRSP (del esporozoito) y SERA 5 (del merozoito) que tienen alta afinidad de unión a células HepG2 y a glóbulos rojos respectivamente (conocidos como cHABPs), han sido modificados (conocidos como mHABPs), sintetizados y evaluados a nivel de respuesta inmune en monos Aotus así como estudiados en su conformación estructural por RMN de 1H. Los resultados muestran que los péptidos nativos no son inmunogénicos, pero pueden inducir altos títulos de anticuerpos cuando sus residuos críticos o sus vecinos son reemplazados por otro con un volumen y masa similar, pero diferente polaridad. El estudio conformacional pone de manifiesto que las estructuras de los péptidos nativos son diferentes de sus péptidos modificados ya sea que muestren regiones estructuradas más cortas o más largas o que no presenten ninguna, en comparación con sus análogos modificados altamente inmunogénicos. Las características estereoquímicas particulares en las cadenas laterales de algunos residuos de aminoácidos de estos péptidos modificados así como los rasgos fisicoquímicos parecen jugar un rol importante en la respuesta inmune apropiada cuando estos fueron inmunizados en grupos de monos Aotus confiriendo un avance al diseño de una vacuna contra malaria totalmente eficaz.

Towards a full cosmological exploitation of cosmic voids

A stately fraction of the Universe volume is dominated by almost empty space. Alongside the luminous filamentary structures that make it up, there are vast and smooth regions that have remained outside the Cosmology spotlight during the past decades: cosmic voids. Although essentially devoid of matter, voids enclose fundamental information about the cosmological framework and have gradually become an effective and competitive cosmological probe. In this Thesis work we present fundamental results about the cosmological exploitation of voids. We focused on the number density of voids as a function of their radius, known as void size function, developing an effective pipeline for its cosmological usage. We proposed a new parametrisation of the most used theoretical void size function to model voids identified in the distribution of biased tracers (i.e. dark matter haloes, galaxies and galaxy clusters), a step of fundamental importance to extend the analysis to real data surveys. We then applied our built methodology to study voids in alternative cosmological scenarios. Firstly we exploited voids with the aim of breaking the degeneracies between cosmological scenarios characterised by modified gravity and the inclusion of massive neutrinos. Secondly we analysed voids in the perspective of the Euclid survey, focusing on the void abundance constraining power on dynamical dark energy models with massive neutrinos. Moreover we explored other void statistics like void profiles and clustering (i.e. the void-galaxy and the void-void correlation), providing cosmological forecasts for the Euclid mission. We finally focused on the probe combination, highlighting the incredible potential of the joint analysis of multiple void statistics and of the combination of the void size function with different cosmological probes. Our results show the fundamental role of the void analysis in constraining the fundamental parameters of the cosmological model and pave the way for future studies on this topic.

The bright routes to five-membered heterocycles: a photoredox catalytic approach

Synthetic chemists constantly strive to develop new methodologies to access complex molecules more sustainably. The recently developed photocatalytic approach results in a valid and greener alternative to the classical synthetic methods. Here we present three protocols to furnish five-membered rings exploiting photoredox catalysis. We firstly obtained 4,5-dihydrofurans (4,5-DHFs) from readily available olefins and α-haloketones employing fac-Ir(ppy)3 as a photocatalyst under blue-light irradiation (Figure 1, top). This transformation resulted very broad in scope, thanks to its mild conditions and the avoidance of stoichiometric amounts of oxidants or reductants. Moreover, similar conditions could lead to β,γ-unsaturated ketones, or highly substituted tetrahydrofurans (THFs) by carefully differentiating the substitution pattern on the starting materials and properly adjusting the reaction parameters. We then turned our attention to the reactivity of allenamides employing analogous photocatalytic conditions to access 2-aminofurans (Figure 1, bottom). α-Haloketones again provided the radical generated by fac-Ir(ppy)3 under visible-light irradiation, which added to the π-system and furnished the cyclic molecule. The addition of a second molecule of the α-haloketone moiety led to the formation of the final highly functionalized furan, which might be further elaborated to afford more complex products. The two works were both supplied with mechanistic investigations supported by experimental and computational methods. As our last project, we developed a methodology to achieve cypentanonyl-fused N-methylpyrrolidines (Figure 2), exploiting N,N-dimethylamines and carboxylic acids as radical sources. In two separated photocatalytic steps, both functionalities are manipulated through the photoredox catalysis by 4CzIPN to add to an α,β-enone system, furnishing the bicyclic product.

Engineering the structures of nanoporous clays with micelles of alkyl polyether surfactants

Composite clay nanostructures (CCNs) were observed in intercalating Laponite clay with alumina in the presence of alkyl polyether surfactants which contain hydrophobic alkyl chains and ether groups. Such nanostructured clays are highly porous solids consisting of randomly orientated clay platelets intercalated with alumina nanoparticles. The pores in the product solids are larger than the dimension of the surfactant molecules, ranging from 2 to 10 nm. This suggests that the micelles of the surfactant molecules, rather than the molecules, act as templates in the synthesis. Interestingly, it is found that the size of the framework pores was directly proportional to the amount of the surfactants in terms of moles, but shows no evident dependence on the size of the surfactant molecules. Broad pore size distributions were observed for the product CCNs. This study demonstrates that introducing surfactants in the pillaring process of clays is a powerful strategy for tailoring the pore structures of nanoporous clays. With this new technique, it is possible to design and engineer such composite clay nanostructures with desired pore and surface properties by the proper choice of surfactant amounts and preparation conditions.

Vanadium-modified molecular sieves: preparation, characterization and catalysis

Vanadium-containing molecular sieves are redox catalysts and are good candidates as substitutes for oxide-supported V2O5 in a number of reactions. These materials have the advantage of presenting better dispersion of vanadium species, as well as shape-selective properties and controllable acidities. They may be prepared by one-pot synthesis or by post-synthesis methods and a number of techniques such as diffuse reflectance UV-visible spectroscopy, 51V nuclear magnetic resonance and electron paramagnetic resonance, to name but a few, have been used to characterize these materials. In this review, methods of preparation of vanadium-modified molecular sieves, their characterization and applications in catalysis are discussed.

Effect of modified clays on the structure and functional properties of biofilms produced with zein

The purpose of this study was to evaluate changes in the structure and some functional properties of biofilms added with modified clays (Cloisite® 15A and Cloisite® 30B) prepared by the casting method. The analysis of the microstructure of the films, scanning electron microscopy (SEM), Optical microscopy (MO), and Infrared Spectroscopy (FTIR) indicated that the addition of clay in the films resulted in the formation of a heterogeneous microstructure, microcomposite or tactoid. Due to the formation of a microcomposite structure, functional properties of the films added with both clays such as opacity, solubility, and permeability to water vapor (PVA), were not better than those of the control film. Thus, it was concluded that although it is possible to produce a film added with modified clays using the casting method, it was not possible to obtain intercalation or exfoliation in a nanocomposite, which would result in improved functional properties.

Organic Synthesis Mediated by Heterogeneous Catalysts

Catalysis is a technologically important field which determines the quality of life in future. Catalyst research in pharmaceutical industry,fine chemical synthesis and emission control demands supported catalysts in bulk quantities.In the present work it was observed that clay supported catalysts mentioned in various chapters could also be used for the synthesis of similar molecules. The K10Ti catalyst can be used for the synthesis similar substituted imidazole derivatives under solvent free conditions and synthetically important Mannich bases of substrates containing various substitutes.Al-pillared saponite can be used for acetalation of other polyhydroxy compounds like glycerol,mannitol etc.Cu-Pd KSF catalyst has found application in C-C bond forming reactions which can be applied to other reactions and similar methods can be adopted for the synthesis of other catalyst by changing the transition metals. Montmorillonite K10 catalysed synthesis of triarylpyridines can be extended to the synthesis tetrasubstuted pyroles.K10Ti can also be utilized for the synthesis of similar heterocycles.

Effect of modified clays on the structure and functional properties of biofilms produced with zein

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Polymerization of ethylene by the tris(pyrazolyl)borate titanium(IV) compound immobilized on MAO-modified silicas

The immobilization of soluble catalyst {Tp(Ms)}TiCl3 (Tp(Ms*)HB(3-mesityl-pyrazolyl)(2)(5-mesityl-pyrazolyl)(-)) on silica and MAO-modified silicas containing 4.0, 8.0 and 23.0 wt.% Al/SiO2 yields active supported catalysts for ethylene polymerization. Among the supported catalysts studied by XRF spectroscopy, higher titanium content was obtained using MAO-modified silica containing 8.0 wt.% Al/SiO2 as support. For the ethylene polymerization reactions carried out in hexane at 60degreesC using a combination of triisobutylaluminum (TiBA) and methylaluminoxane (MAO) (1:1), the activities varied between 24.4 and 113.5 kg of PE/mol [Ti] h. The highest activity is reached using MAO-modified silica containing 4.0 wt.% Al/SiO2 as support. The viscosity-average molecular weights ((M) over bar (v)) of the PE's produced with the supported catalysts varying from 1.44 to 9.94 x 10(5) g/mol with melting temperatures in the range of 125-140degreesC. The use of other Lewis acid cocatalysts, including TiBA, diethylaluminium chloride (DEAC), and trimethylaluminum (TMA) resulted also in the formation of active catalysts for ethylene polymerization. However, the activities are lower than that one using a combination of TiBA and MAO. The viscosity-average molecular weights (R,) of PE's are influenced by varying the cocatalysts as well as the Al/Ti molar ratio. The supported catalyst generated in situ under ethylene atmosphere is roughly four times more active than supported one containing 4.0 wt.% Al/SiO2. (C) 2003 Elsevier B.V. All rights reserved.

Structure of a novel class II phospholipase D: Catalytic cleft is modified by a disulphide bridge

Phospholipases D (PLDs) are principally responsible for the local and systemic effects of Loxosceles envenomation including dermonecrosis and hemolysis. Despite their clinical relevance in loxoscelism, to date, only the SMase I from Loxosceles laeta, a class I member, has been structurally characterized. The crystal structure of a class II member from Loxosceles intermedia venom has been determined at 1.7. Å resolution. Structural comparison to the class I member showed that the presence of an additional disulphide bridge which links the catalytic loop to the flexible loop significantly changes the volume and shape of the catalytic cleft. An examination of the crystal structures of PLD homologues in the presence of low molecular weight compounds at their active sites suggests the existence of a ligand-dependent rotamer conformation of the highly conserved residue Trp230 (equivalent to Trp192 in the glycerophosphodiester phosphodiesterase from Thermus thermophofilus, PDB code: 1VD6) indicating its role in substrate binding in both enzymes. Sequence and structural analyses suggest that the reduced sphingomyelinase activity observed in some class IIb PLDs is probably due to point mutations which lead to a different substrate preference. © 2011 Elsevier Inc.