Reaction Kinetics in the Production of Pd Nanoparticles in Reverse Microemulsions. Effect on Particle Size

In the synthesis of metallic nanoparticles in microemulsions, we hypothesized that particle size is mainly controlled by the reaction rate. Thus, the changes observed on the particle sizes as reaction conditions, such as concentrations, temperature, type of surfactant used, etc., are varied should not be correlated directly to the modification of those conditions but indirectly to the changes they produce on the reaction rates. By means of time resolved UV-vis spectroscopy, we measured the reaction rates in the production of Pd nanoparticles inside microemulsions at different reactant concentrations, keeping all the other parameters constant. The measured reaction rates were then correlated with the particle sizes measured by transmission electron microscopy (TEM). We found that nanoparticle size increases linearly as the reaction rates increases, independently of the actual reactant concentrations. We proposed that the kinetics is controlled mainly by the diffusion of the reducing agent through the surfactant monolayer covering the microemulsion membrane. With this model, we predicted that particle size should depend indirectly, via the reaction kinetics, on the micelle radius (v0 ~ r^-3), the water volume (v0~vw^3) and the total microemulsion volume (v0~vT^-3), and temperature (Arrhenius). Some of these predictions were explored in this article

The catalytic mechanism of steroidogenic cytochromes P450 from all-atom simulations: Entwinement with membrane environment, redox partners, and post-transcriptional regulation

Cytochromes P450 (CYP450s) promote the biosynthesis of steroid hormones with major impact on the onset of diseases such as breast and prostate cancers. By merging distinct functions into the same catalytic scaffold, steroidogenic CYP450s enhance complex chemical transformations with extreme efficiency and selectivity. Mammalian CYP450s and their redox partners are membrane-anchored proteins, dynamically associating to form functional machineries. Mounting evidence signifies that environmental factors are strictly intertwined with CYP450s catalysis. Atomic-level simulations have the potential to provide insights into the catalytic mechanism of steroidogenic CYP450s and on its regulation by environmental factors, furnishing information often inaccessible to experimental means. In this review, after an introduction of computational methods commonly employed to tackle these systems, we report the current knowledge on three steroidogenic CYP450s\u2014CYP11A1, CYP17A1, and CYP19A1\u2014endowed with multiple catalytic functions and critically involved in cancer onset. In particular, besides discussing their catalytic mechanisms, we highlight how the membrane environment contributes to (i) regulate ligand channeling through these enzymes, (ii) modulate their interactions with specific protein partners, (iii) mediate post-transcriptional regulation induced by phosphorylation. The results presented set the basis for developing novel therapeutic strategies aimed at fighting diseases originating from steroid metabolism dysfunction

XPySom: High-performance self-organizing maps

In this paper, we introduce XPySom, a new open-source Python implementation of the well-known Self-Organizing Maps (SOM) technique. It is designed to achieve high performance on a single node, exploiting widely available Python libraries for vector processing on multi-core CPUs and GP-GPUs. We present results from an extensive experimental evaluation of XPySom in comparison to widely used open-source SOM implementations, showing that it outperforms the other available alternatives. Indeed, our experimentation carried out using the Extended MNIST open data set shows a speed-up of about 7x and 100x when compared to the best open-source multi-core implementations we could find with multi-core and GP-GPU acceleration, respectively, achieving the same accuracy levels in terms of quantization error

Larga batalla de un paciente con sida y tuberculosis recurrente: ¿reinfección o reactivación?

The advent of Mycobacterium tuberculosis strain genotyping has allowed differentiation between disease relapse and exogenous re-infection. We report here a remarkable case of multiply recurrent tuberculosis in a patient living with HIV. Between 1995 and 2009, a young HIV-infected intravenous drug user, who was reluctant to comply with anti-retroviral treatment, underwent at least five tuberculosis episodes caused by three distinct M. tuberculosis strains sharply differentiated by drug susceptibility profile, genotype and infectious source. Eventually, the patient died during a relapse of tuberculosis due to a notorious multidrug-resistant outbreak-strain, which infected him during a prolonged hospitalization in the epicentre of such outbreak. Whether recurrent tuberculosis is due to a new infection or to reactivation of a previous one is a century-long controversial question. In our patient, both conditions alternated throughout his 15 years of living with HIV. Cases such as this might not be exceptional in certain underprivileged suburban areas of Argentina and should raise concern over three pending issues in tuberculosis control policies, namely secondary preventive therapy, institutional infection control and patient follow-up throughout the health network system.La genotipificación de aislamientos clínicos de Mycobacterium tuberculosis permite diferenciar entre recaída y reinfección exógena. Presentamos un notable caso de tuberculosis recurrente asociado a sida. Entre 1995 y 2009, un usuario de drogas ilegales por vía endovenosa, con infección por el VIH pero reacio al tratamiento antirretroviral, sufrió cinco episodios de tuberculosis causados por tres cepas de M. tuberculosis. Las cepas se diferenciaron por los genotipos, los perfiles de sensibilidad a antibióticos y las fuentes de infección. El paciente murió de tuberculosis por una cepa multirresistente, responsable de un extenso brote en Argentina, que lo infectó durante una prolongada internación en el hospital que fue el epicentro de dicho brote. La controversia sobre el origen de la tuberculosis recurrente –reinfección o reactivación– lleva ya un siglo y continúa vigente. En el caso que aquí se describe, las dos situaciones se alternaron a lo largo de los 15 años de lucha contra el sida que atravesó este paciente. Esta situación puede no ser excepcional en áreas suburbanas desfavorecidas de Argentina, y pone en evidencia tres temas insuficientemente atendidos en nuestro medio: el tratamiento preventivo de la tuberculosis secundaria, el control de su transmisión en hospitales y cárceles, y el seguimiento de los pacientes a través del sistema de salud.Fil: Reniero, A.. Hospital Municipal de San Isidro; ArgentinaFil: Beltrán, M.. Hospital Municipal de San Isidro; ArgentinaFil: de Kantor, I. N.. PAHO/WHO consultant; ArgentinaFil: Ritacco, Gloria Viviana. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Dirección Nacional de Institutos de Investigación. Administración Nacional de Laboratorios e Institutos de Salud. Instituto Nacional de Enfermedades Infecciosas; Argentin

Using Self-Organizing Maps for the Behavioral Analysis of Virtualized Network Functions

Detecting anomalous behaviors in a network function virtualization infrastructure is of the utmost importance for network operators. In this paper, we propose a technique, based on Self-Organizing Maps, to address such problem by leveraging on the massive amount of historical system data that is typically available in these infrastructures. Indeed, our method consists of a joint analysis of system-level metrics, provided by the virtualized infrastructure monitoring system and referring to resource consumption patterns of the physical hosts and the virtual machines (or containers) that run on top of them, and application-level metrics, provided by the individual virtualized network functions monitoring subsystems and related to the performance levels of the individual applications. The implementation of our approach has been validated on real data coming from a subset of the Vodafone infrastructure for network function virtualization, where it is currently employed to support the decisions of data center operators. Experimental results show that our technique is capable of identifying specific points in space (i.e., components of the infrastructure) and time of the recent evolution of the monitored infrastructure that are worth to be investigated by human operators in order to keep the system running under expected conditions

Behavioral analysis for virtualized network functions: A som-based approach

In this paper, we tackle the problem of detecting anomalous behaviors in a virtualized infrastructure for network function virtualization, proposing to use self-organizing maps for analyzing historical data available through a data center. We propose a joint analysis of system-level metrics, mostly related to resource consumption patterns of the hosted virtual machines, as available through the virtualized infrastructure monitoring system, and the application-level metrics published by individual virtualized network functions through their own monitoring subsystems. Experimental results, obtained by processing real data from one of the NFV data centers of the Vodafone network operator, show that our technique is able to identify specific points in space and time of the recent evolution of the monitored infrastructure that are worth to be investigated by a human operator in order to keep the system running under expected conditions

Unraveling the impact of cysteine-to-serine mutations on the structural and functional properties of Cu(I)-binding proteins

Appropriate maintenance of Cu(I) homeostasis is an essential requirement for proper cell function because its misregulation induces the onset of major human diseases and mortality. For this reason, several research efforts have been devoted to dissecting the inner working mechanism of Cu(I)-binding proteins and transporters. A commonly adopted strategy relies on mutations of cysteine residues, for which Cu(I) has an exquisite complementarity, to serines. Nevertheless, in spite of the similarity between these two amino acids, the structural and functional impact of serine mutations on Cu(I)-binding biomolecules remains unclear. Here, we applied various biochemical and biophysical methods, together with all-atom simulations, to investigate the effect of these mutations on the stability, structure, and aggregation propensity of Cu(I)-binding proteins, as well as their interaction with specific partner proteins. Among Cu(I)-binding biomolecules, we focused on the eukaryotic Atox1-ATP7B system, and the prokaryotic CueR metalloregulator. Our results reveal that proteins containing cysteine-to-serine mutations can still bind Cu(I) ions; however, this alters their stability and aggregation propensity. These results contribute to deciphering the critical biological principles underlying the regulatory mechanism of the in-cell Cu(I) concentration, and provide a basis for interpreting future studies that will take advantage of cysteine-to-serine mutations in Cu(I)-binding systems

Equilibrium and dynamic surface properties of trisiloxane aqueous solutions. Part 1. Experimental results

Tensiometry, ellipsometry and Brewster angle microscopy were used to measure equilibrium and dynamic surface tension, as well as surface adsorption, of aqueous solutions of trisiloxane surfactants. Complex adsorption curves, including inflection points, have been found for the surfactants with long etoxylated chains. Surface aggregates at the liquid–air interfaces have been detected for the trisiloxanes that show superspreading behaviour onto moderately hydrophobic surfaces, while no aggregates were detected for the shorter trisiloxanes. The latter suggests that those surface aggregates may act as reservoirs of surfactant molecules to maintain the required surface tension in the course of spreading