Your browser doesn't support javascript.
loading
Show: 20 | 50 | 100
Results 1 - 20 de 69
Filter
1.
Int J Mol Sci ; 22(10)2021 May 17.
Article in English | MEDLINE | ID: mdl-34067817

ABSTRACT

BACKGROUND: Exposure to intermittent hypoxia has been demonstrated to be an efficient tool for hypoxic preconditioning, preventing damage to cells and demonstrating therapeutic benefits. We aimed to evaluate the effects of respiratory intermittent hypobaric hypoxia (IHH) to avoid brain injury caused by exposure to acute severe hypoxia (ASH). METHODS: biomarkers of oxidative damage, mitochondrial apoptosis, and transcriptional factors in response to hypoxia were assessed by Western blot and immunohistochemistry in brain tissue. Four groups of rats were used: (1) normoxic (NOR), (2) exposed to ASH (FiO2 7% for 6 h), (3) exposed to IHH for 3 h per day over 8 days at 460 mmHg, and (4) ASH preconditioned after IHH. RESULTS: ASH animals underwent increased oxidative-stress-related parameters, an upregulation in apoptotic proteins and had astrocytes with phenotype forms compatible with severe diffuse reactive astrogliosis. These effects were attenuated and even prevented when the animals were preconditioned with IHH. These changes paralleled the inhibition of NF-κB expression and the increase of erythropoietin (EPO) levels in the brain. CONCLUSIONS: IHH exerted neuroprotection against ASH-induced oxidative injury by preventing oxidative stress and inhibiting the apoptotic cascade, which was associated with NF-κB downregulation and EPO upregulation.


Subject(s)
Hypoxia/metabolism , Hypoxia/prevention & control , Oxidative Stress/physiology , Animals , Antioxidants/pharmacology , Apoptosis/physiology , Astrocytes/metabolism , Brain/metabolism , Erythropoietin/pharmacology , Gliosis/metabolism , Male , Mitochondria/metabolism , NF-kappa B/metabolism , Neurons/metabolism , Neuroprotection/physiology , Oxidative Stress/drug effects , Rats , Rats, Sprague-Dawley
2.
Phys Chem Chem Phys ; 23(8): 4615-4623, 2021 Mar 04.
Article in English | MEDLINE | ID: mdl-33620369

ABSTRACT

Artificial neural networks (ANNs) were developed to accurately predict the self-diffusion constants for pure components in liquid, gas and super critical phases. The ANNs were tested on an experimental database of 6625 self-diffusion constants for 118 different chemical compounds. The presence of multiple phases results in a heavy skew in the distribution of diffusion constants and multiple approaches were used to address this challenge. First, an ANN was developed with the raw diffusion values to assess what the main drawbacks of this direct method were. The first approach for improving the predictions involved taking the log 10 of diffusion to provide a more uniform distribution and reduce the range of target output values used to develop the ANN. The second approach involved developing individual ANNs for each phase using the raw diffusion values. Results show that the log transformation leads to a model with the best self-diffusion constant predictions and an overall average absolute deviation (AAD) of 6.56%. The resultant ANN is a generalized model that can be used to predict diffusion across all three phases and over a diverse group of compounds. The importance of each input feature was ranked using a feature addition method revealing that the density of the compound has the largest impact on the ANN prediction of self-diffusion constants in pure compounds.

3.
Commun Chem ; 4(1): 139, 2021 Sep 29.
Article in English | MEDLINE | ID: mdl-36697640

ABSTRACT

Efficient conversion of methane to value-added products such as olefins and aromatics has been in pursuit for the past few decades. The demand has increased further due to the recent discoveries of shale gas reserves. Oxidative and non-oxidative coupling of methane (OCM and NOCM) have been actively researched, although catalysts with commercially viable conversion rates are not yet available. Recently, [Formula: see text] (SFMO-075Fe) has been reported to activate methane in an electrochemical OCM (EC-OCM) set up with a C2 selectivity of 82.2%1. However, alkaline earth metal-based materials are known to suffer chemical instability in carbon-rich environments. Hence, here we evaluated the chemical stability of SFMO in carbon-rich conditions with varying oxygen concentrations at temperatures relevant for EC-OCM. SFMO-075Fe showed good methane activation properties especially at low overpotentials but suffered poor chemical stability as observed via thermogravimetric, powder XRD, and XPS measurements where SrCO3 was observed to be a major decomposition product along with SrMoO3 and MoC. Nevertheless, our study demonstrates that electrochemical methods could be used to selectively activate methane towards partial oxidation products such as ethylene at low overpotentials while higher applied biases result in the complete oxidation of methane to carbon dioxide and water.

4.
J Chem Phys ; 153(3): 034102, 2020 Jul 21.
Article in English | MEDLINE | ID: mdl-32716182

ABSTRACT

Different machine learning (ML) methods were explored for the prediction of self-diffusion in Lennard-Jones (LJ) fluids. Using a database of diffusion constants obtained from the molecular dynamics simulation literature, multiple Random Forest (RF) and Artificial Neural Net (ANN) regression models were developed and characterized. The role and improved performance of feature engineering coupled to the RF model development was also addressed. The performance of these different ML models was evaluated by comparing the prediction error to an existing empirical relationship used to describe LJ fluid diffusion. It was found that the ANN regression models provided superior prediction of diffusion in comparison to the existing empirical relationships.

6.
J Alzheimers Dis ; 65(4): 1469-1483, 2018.
Article in English | MEDLINE | ID: mdl-30175978

ABSTRACT

Many experimental studies show that erythropoietin (EPO) has a neuroprotective action in the brain. EPO in acute and chronic neurological disorders, particularly in stroke, traumatic brain injury, Alzheimer's disease, Parkinson's disease, and amyotrophic lateral sclerosis, has neuroprotective effects. We previously reported the neuroprotective effect of NeuroEPO, a low sialic form of EPO, against oxidative stress induced by glutamate excitotoxicity. In this paper, we analyze the effect of NeuroEPO against apoptosis induced by glutamate excitotoxicity in primary neuronal cultures obtained from the forebrains of Wistar rat embryos after 17 days of gestation. Excitotoxicity was induced after nine days of in vitro culture by treatment with a culture medium containing 100µM glutamate for 15 min. To withdraw glutamate, a new medium containing 100 ng NeuroEPO/mL was added. Apoptosis was analyzed after 24 h. Images obtained by phase contrast microscopy show that neurons treated with glutamate exhibit cell body shrinkage, loss of dendrites that do not make contact with neighboring cells, and that NeuroEPO was able to preserve the morphological characteristics of the control. Immunocytochemistry images show that the culture is essentially pure in neurons; that glutamate causes cell mortality, and that this is partially avoided when the culture medium is supplemented with NeuroEPO. Activation of intrinsic apoptotic pathways was analyzed. The decreases in Bcl-2/Bax ratio, increase in the release of cytochrome c, and in the expression and activity of caspase-3 observed in cells treated with glutamate, were restored by NeuroEPO. The results from this study show that NeuroEPO protects cortical neurons from glutamate-induced apoptosis via upregulation of Bcl-2 and inhibit glutamate-induced activation of caspase-3.


Subject(s)
Erythropoietin/pharmacology , Excitatory Amino Acid Agonists/pharmacology , Glutamic Acid/toxicity , Neurons/drug effects , Neuroprotective Agents/pharmacology , Anilides/pharmacology , Animals , Caspase 3/metabolism , Cells, Cultured , Cerebral Cortex/cytology , Cytochromes c/metabolism , Embryo, Mammalian , Glial Fibrillary Acidic Protein/metabolism , Microtubule-Associated Proteins/metabolism , Oligopeptides/pharmacology , Proto-Oncogene Proteins c-bcl-2/metabolism , Rats , Rats, Wistar , Time Factors , bcl-2-Associated X Protein/metabolism
7.
Phys Chem Chem Phys ; 20(21): 14679-14687, 2018 May 30.
Article in English | MEDLINE | ID: mdl-29770397

ABSTRACT

We report herein a density functional theory study of the nitrogen electroreduction and hydrogen evolution reactions on cubic molybdenum carbide (MoC) in order to investigate the viability of using this material as an electro-catalyst for ammonia synthesis. Free energy diagrams for associative and dissociative Heyrovsky mechanisms showed that nitrogen reduction on cubic MoC(111) can proceed via an associative mechanism and that small negative potentials of -0.3 V vs. standard hydrogen electrode can onset the reduction of nitrogen to ammonia. Kinetic volcano plots for hydrogen evolution showed that the MoC[110] surface is expected to have a high rate for the hydrogen evolution reaction, which could compete with the reduction of nitrogen on cubic MoC. The comparison between the adsorption energies of H-adatoms and N-adatoms also shows that at low potentials adsorption of hydrogen atoms competes with nitrogen adsorption on all the MoC surfaces except the MoC(111) surface. The hydrogen evolution and accumulation of H-adatoms can be mitigated by introducing carbon vacancies i.e. increasing the ratio of metal to carbon atoms, which will significantly increase the affinity of the catalytic surface for both nitrogen molecules and N-adatoms.

8.
J Comput Chem ; 35(26): 1921-9, 2014 Oct 05.
Article in English | MEDLINE | ID: mdl-25164265

ABSTRACT

The structural equilibrium parameters, the adsorption energies, and the vibrational frequencies of the nitrogen molecule and the hydrogen atom adsorbed on the (111) surface of rhodium have been investigated using different generalized-gradient approximation (GGA), nonlocal correlation, meta-GGA, and hybrid functionals, namely, Perdew, Burke, and Ernzerhof (PBE), Revised-RPBE, vdW-DF, Tao, Perdew, Staroverov, and Scuseria functional (TPSS), and Heyd, Scuseria, and Ernzerhof (HSE06) functional in the plane wave formalism. Among the five tested functionals, nonlocal vdW-DF and meta-GGA TPSS functionals are most successful in describing energetics of dinitrogen physisorption to the Rh(111) surface, while the PBE functional provides the correct chemisorption energy for the hydrogen atom. It was also found that TPSS functional produces the best vibrational spectra of the nitrogen molecule and the hydrogen atom on rhodium within the harmonic formalism with the error of -2.62 and -1.1% for the N-N stretching and Rh-H stretching frequency. Thus, TPSS functional was proposed as a method of choice for obtaining vibrational spectra of low weight adsorbates on metallic surfaces within the harmonic approximation. At the anharmonic level, by decoupling the Rh-H and N-N stretching modes from the bulk phonons and by solving one- and two-dimensional Schrödinger equation associated with the Rh-H, Rh-N, and N-N potential energy we calculated the anharmonic correction for N-N and Rh-H stretching modes as -31 cm(-1) and -77 cm(-1) at PBE level. Anharmonic vibrational frequencies calculated with the use of the hybrid HSE06 function are in best agreement with available experiments.

9.
Phys Chem Chem Phys ; 16(7): 3014-26, 2014 Feb 21.
Article in English | MEDLINE | ID: mdl-24394549

ABSTRACT

We used density functional theory to study the electrochemical conversion of nitrogen to ammonia on the (001), (100/010), (101), and (111) surfaces of γ-Mo2N. Based on the calculated free energy profiles for the reduction of nitrogen by the associative and dissociative mechanisms, reactivity was found to decrease in the order (111) > (101) > (100/010) ≈ (001). Namely, the cell potentials needed to drive the reduction to ammonia increase in the following order: -0.7 V on (111), -1.2 V on (101), and -1.4 V on (100/010) and (001) surfaces. The (111) surface was found to be the most reactive for nitrogen due to (i) its ability to adsorb the N2 in the side-on position which activates N-N bonding and (ii) its high affinity for N-adatoms which also prevents accumulation of H-adatoms on the catalytic surface at low cell potentials. We have also calculated vibrational frequencies of different NxHy species adsorbed on various γ-Mo2N surfaces. The frequencies are found to depend strongly on the type of the binding sites available on the crystal facets. A comparison of the calculated frequencies with the frequencies of the corresponding species in transition metal complexes and other metal surfaces shows that the frequencies of several signature modes fall in a similar region and might be used to assign the spectra of hydrogen and nitrogen containing surface species on different metal surfaces.

11.
Montevideo; Plus-Ultra Ediciones; 2013. 359 p.
Monography in Spanish | LILACS | ID: lil-759711
12.
J Am Chem Soc ; 133(51): 20672-5, 2011 Dec 28.
Article in English | MEDLINE | ID: mdl-22087502

ABSTRACT

Sintering of nanoparticles (NPs) of Ni supported on MgAl(2)O(4) was monitored in situ using transmission electron microscopy (TEM) during exposure to an equimolar mixture of H(2) and H(2)O at a pressure of 3.6 mbar at 750 °C, conditions relevant to methane steam reforming. The TEM images revealed an increase in the mean particle size due to disappearance of smaller, immobile NPs and the resultant growth of the larger NPs. A new approach for predicting the long-term sintering of NPs is presented wherein microscopic observations of the ripening of individual NPs (over a span of a few seconds) are used to extract energetic parameters that allow a description of the collective behavior of the entire population of NPs (over several tens of minutes).

13.
J Hazard Mater ; 190(1-3): 125-32, 2011 Jun 15.
Article in English | MEDLINE | ID: mdl-21435779

ABSTRACT

In this article, selective and sensitive detection of trace amounts of pentaerythritol tetranitrate (PETN), 2,4,6-trinitrotoluene (TNT) and cyclotrimethylenetrinitramine (RDX) is demonstrated. The screening system is based on a sampling/concentrator front end and electrochemical potentiometric gas sensors as the detector. Preferential hydrocarbon and nitrogen oxide(s) mixed potential sensors based on lanthanum strontium chromite and Pt electrodes with yttria stabilized zirconia (YSZ) solid electrolyte were used to capture the signature of the explosives. Quantitative measurements based on hydrocarbon and nitrogen oxide sensor responses indicated that the detector sensitivity scaled proportionally with the mass of the explosives (1-3 µg). Moreover, the results showed that PETN, TNT, and RDX samples could be discriminated from each other by calculating the ratio of nitrogen oxides to hydrocarbon integrated area under the peak. Further, the use of front-end technology to collect and concentrate the high explosive (HE) vapors make intrinsically low vapor pressure of the HE less of an obstacle for detection while ensuring higher sensitivity levels. In addition, the ability to use multiple sensors each tuned to basic chemical structures (e.g., nitro, amino, peroxide, and hydrocarbon groups) in HE materials will permit the construction of low-cost detector systems for screening a wide spectrum of explosives with lower false positives than present-day technologies.


Subject(s)
Explosive Agents/analysis , Potentiometry/methods , Electrodes , Electrolytes , Gases , Hydrocarbons , Nitrogen Oxides , Pentaerythritol Tetranitrate/analysis , Triazines/analysis , Trinitrotoluene/analysis
14.
Chem Commun (Camb) ; 46(40): 7489-91, 2010 Oct 28.
Article in English | MEDLINE | ID: mdl-20848022

ABSTRACT

A new non-precious metal oxygen reduction catalyst was developed via heat treatment of in situ polymerized polyaniline onto TiO(2) particles in the presence of Fe species. The TiO(2) provides for improved performance relative to a carbon black-based catalyst and, at a high catalyst loading, allows for reducing the performance gap between non-precious-metal catalyst and Pt/C to ca. 20 mV in RDE testing.

16.
17.
Interciencia ; 34(3): 219-224, mar. 2009. tab
Article in English | LILACS | ID: lil-630727

ABSTRACT

The only extant version of the first lecture course given by Claude Bernard on Experimental Physiology during the winter period of 1847-48 in Collège de France, substituting Magendie, is presented herein. The prominent Paris-graduated physician from Uruguay, Teodoro M. Vilardebó, attended the 46 lectures, wrote them down and transcribed them into a manuscript that he brought back to and kept in Montevideo in 1853. Mañé-Garzón uncovered it in 1987. These Bernard’s lectures review practically all physiology at the beginning of his career, while in later courses, he covered selected themes of experimental physiology and medicine and general scientific subjects at greater depth. Comparison of Bernard’s initial course with his later ones illustrates general physiology’s progress in the more than 35 years of his successful scientific life. The manuscript sheds new light into Bernard’s scientific activity and personality.


Se presenta la única versión existente del primer curso sobre Fisiología Experimental dictado, en sustitución de Magendie, por Claude Bernard en el invierno 1847-1848 en el Collège de France. El destacado médico uruguayo graduado en París, Teodoro M. Vilardebó, asistió a las 46 lecciones, tomó apuntes y los transcribió a un manuscrito que trajo de vuelta en 1853 y conservó en Montevideo. Mañé-Garzón lo descubrió en 1987. Estas lecciones de Bernard revelan prácticamente toda la fisiología de comienzos de su carrera, mientras en cursos posteriores cubrió en mayor profundidad tópicos selectos de la fisiología y la medicina experimentales, así como temas científicos generales. La comparación del curso inicial de Bernard con otros posteriores ilustra el progreso de la fisiología general durante los más de 35 años de su exitosa vida científica. El manuscrito vierte nueva luz acerca de la actividad científica y la personalidad de Bernard.


Apresenta-se a única versão existente do primeiro curso sobre Fisiología Experimental ditado, em sustituição de Magendie, por Claude Bernard no inverno 1847-1848 no Collège de France. O destacado médico uruguaio graduado em París, Teodoro M. Vilardebó, assistiu às 46 lições, anotou e os transcreveu a um manuscrito que trouxe de volta en 1853 e conservou em Montevideo. Mañé-Garzón o descobriu em 1987. Estas lições de Bernard revelam práticamente toda a fisiologia do princípio da sua carreira, enquanto que em cursos posteriores cubriu em maior profundidade tópicos seletos da fisiologia e a medicina experimentais, assim como temas científicos gerais. A comparação do curso inicial de Bernard com outros posteriores ilustra o progresso da fisiologia geral durante mais de 35 anos de sua exitosa vida científica. O manuscrito verte nova luz sobre da atividade científica e a personalidade de Bernard.

SELECTION OF CITATIONS
SEARCH DETAIL
...