Identification of a quenching species in ruthenium tris-bipyridine electroluminescent devices

We have used matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry and micro-Raman spectroscopy to identify a quenching species that is formed during operation of [Ru(bpy)3]2+ electroluminescent devices. We identify this performance-degrading product to be the oxo-bridged dimer [(bpy)2(H2O)RuORu(OH2)(bpy)2]4+ and show this dimer to be an effective quencher of device luminescence. This work is the first to detect a specific chemical degradation product formed during iTMC OLED operation.     

Effective construction of Poincar\'e--Bendixson regions

This paper deals with the problem of location and existence of limit cycles for real planar polynomial differential systems. We provide a method to construct Poincar\''e--Bendixson regions by using transversal curves, that enables us to prove the existence of a limit cycle that has been numerically detected. We apply our results to several known systems, like the Brusselator one or some Li\''{e}nard systems, to prove the existence of the limit cycles and to locate them very precisely in the phase space. Our method, combined with some other classical tools can be applied to obtain sharp bounds for the bifurcation values of a saddle-node bifurcation of limit cycles, as we do for the Rychkov system.     

ZnO Nanoparticles for Photocatalytic Application in Alkali-Activated Materials

This paper reports an Alkali-Activated Materials (AAM) using two different precursors, metakaolin and a metallurgical slag with photocatalytic zinc oxide nanoparticles, as novel photocatalytic composites. The photodegradation performance of the composites using methylene blue (MB) dye as a wastewater model was investigated by ultraviolet radiations (UV-vis) spectroscopy. Adsorption in dark conditions and photodegradation under UV irradiation are the mechanisms for removing MB dye. The pseudo-first-order kinetic and pseudo-second-order kinetic models were employed, and the experimental data agreed with the pseudo-second-order model in both cases with UV and without UV irradiations. As new photocatalytic materials, these composites offer an alternative for environmental applications.     

Evaluation of damage induced by high irradiation levels on α-Ni-Ni3Si eutectic structure

Diluted alloys of the binary system Ni–Si have been used as target of beam of ions, electrons, neutrons and so on because in this kind of alloy occurs transformations order–disorder, when the temperature is raised. This fact has permitted to evaluate the phenomena associated with the damage induced by irradiation (DII). The results of these works have been employed to understand the behavior under irradiation of complex alloys and to evaluate the reliability of the results of mathematical simulation of the evolution of the DII. The interest in the alloy system Ni-Si has been reborn due to the necessity of developing materials, which have better resistance against the corrosion on more aggressive environments such as those generated on the nuclear power plants or those that exist out of the Earth's atmosphere. Now, a growing interest to use concentrated alloys of this binary system on diverse fields of the materials science has been taking place because up to determined concentration of silicon, a regular eutectic is formed, and this fact opens the possibility to develop lamellar composite material by directional solidification. However, nowadays, there is a lack of fundamental knowledge about the behavior of this type of lamellar structure under aggressive environments, like those mentioned before. Hence, the task of this work is to evaluate the effect that has the irradiation over the microstructure of the concentrated alloy Ni22at%Si. The dendritic region of the hypereutectic alloy consists of an intermetallic phase Ni₃Si, whereas the interdendritic region is formed by the alternation of lamellas of solid solution α-Ni and intermetallic phase Ni₃Si. Such kind of microstructure has the advantage to get information of the DII over different phases individually, and at the same time, about of the microstructure influence over the global damage in the alloy. The hypereutectic Ni22at%Si alloy was irradiated perpendicularly to its surface, with 3.66?MeV – Ni ions up to 380?dpa at 650°C in a Tandetron linear accelerator. The level of irradiation dose was chosen similar to the irradiation conditions of the next-generation nuclear reactors. The theoretical maximum depth of the DII (maximum depth of damage (MDD)) was calculated as 1.35?µm using the SRIM-2013 program; the laminar microstructure of the eutectic was simulated using the lattice parameters of the eutectic before irradiation. The experimental MDD was 1.47?µm, as determined through transmission electron microscope (TEM) images and the DII was characterized using µX-ray diffraction and TEM. The elimination of cubic phase of the intermetallic Ni₃Si, the suppression of lamellae of the α-Ni phase, the generation of dislocation loops and lines, all of these changes generated by the irradiation are clear evidences that the DII was severe. Based on theoretical and experimental evidence, we propose that the amount of phases, alternate of lamellae with different chemical concentrations of silicon and lamellae spatial distribution have a direct relation with the severe evolution of the DII.     

Proof‐of‐Concept Studies Directed toward the Formation of Metallic Ag Nanostructures from Ag3PO4 Induced by Electron Beam and Femtosecond Laser

In this work, for the first time, the instantaneous nucleation and growth processes of Ag nanoparticles on Ag₃PO₄ mediated by femtosecond laser pulses are reported and analyzed. The investigated samples are pure Ag₃PO₄ sample, electron‐irradiated Ag₃PO₄ sample, and laser‐irradiated sample. Complete characterization of the samples is performed using X‐ray diffraction (XRD), Rietveld refinements, field emission scanning electron microscopy, and energy dispersive spectroscopy (EDS). XRD confirms that the irradiated surface layer remains crystalline, and according to EDS analysis, the surface particles are composed primarily of Ag nanoparticles. This method not only offers a one‐step route to synthesize Ag nanoparticles using laser‐assisted irradiation with particle size control, but also reports a complex process involving the formation and subsequent growth of Ag nanoparticles through an unexpected additive‐free in situ fabrication process.     

Tuning of size and shape of Au–Pt nanocatalysts for direct methanol fuel cells

In this article, we report the precise control of the size, shape, and surface morphology of Au–Pt nanocatalysts (cubes, blocks, octahedrons, and dogbones) synthesized via a seed-mediated approach. Gold “seeds” of different aspect ratios (1–4.2), grown by a silver-assisted approach, were used as templates for high-yield production of novel Au–Pt nanocatalysts at a low temperature (40 °C). Characterization by electron microscopy (SEM, TEM, HRTEM), energy dispersive X-ray analysis, UV–Vis spectroscopy, zeta-potential (surface charge), atomic force microscopy, X-ray photoelectron spectroscopy, and inductively coupled plasma mass spectrometry were used to better understand their physico-chemical properties, preferred reactivities and underlying nanoparticle growth mechanism. A rotating disk electrode was employed to evaluate the Au–Pt nanocatalysts electrochemical performance in the oxygen reduction reaction (ORR) and the methanol oxidation reaction of direct methanol fuel cells. The results indicate the Au–Pt dogbones are partially and in some cases completely unaffected by methanol poisoning during the evaluation of the ORR. The ORR performance of the octahedron particles in the absence of MeOH is superior to that of the Au–Pt dogbones and Pt-black; however, its performance is affected by the presence of MeOH.     

Novel rearrangement of N-enoyl oxazolidinethiones to N-substituted 1,3-thiazine-2,4-diones promoted by NbCl5

NbCl₅ has been employed as promoter of a novel rearrangement to afford chiral N-substituted 1,3-thiazine-2,4-diones with one or two new stereogenic centers from di- and trisubstituted N-enoyl oxazolidinethiones. The trisubstituted E-isomers provide the anti-diastereomers mainly.     

Stereoselective Michael addition of 6-amino-1,3-dimethyl-2,4-pyrimidinedione to the exocyclic methylene of three sesquiterpene lactones. 1H and 13C NMR evidence of a new C-C bond and lactam formation

The Stereoselective addition of the pyrimidine derivative 1 to the exocyclic methylene of the α,β unsaturated dehydrocostus lactone 2, Ivalin acetate 3 and Zaluzanin A diacetate 4, was achieved resulting in a new C-C bond formation. In the cases of compounds 3 and 4, after the addition, the lactone was cleaved followed by reclosure into a lactam ring system.     

Machine Learning Models and Statistical Complexity to Analyze the Effects of Posture on Cerebral Hemodynamics

The mechanism of cerebral blood flow autoregulation can be of great importance in diagnosing and controlling a diversity of cerebrovascular pathologies such as vascular dementia, brain injury, and neurodegenerative diseases. To assess it, there are several methods that use changing postures, such as sit-stand or squat-stand maneuvers. However, the evaluation of the dynamic cerebral blood flow autoregulation (dCA) in these postures has not been adequately studied using more complex models, such as non-linear ones. Moreover, dCA can be considered part of a more complex mechanism called cerebral hemodynamics, where others (CO₂ reactivity and neurovascular-coupling) that affect cerebral blood flow (BF) are included. In this work, we analyzed postural influences using non-linear machine learning models of dCA and studied characteristics of cerebral hemodynamics under statistical complexity using eighteen young adult subjects, aged 27 ± 6.29 years, who took the systemic or arterial blood pressure (BP) and cerebral blood flow velocity (BFV) for five minutes in three different postures: stand, sit, and lay. With models of a Support Vector Machine (SVM) through time, we used an AutoRegulatory Index (ARI) to compare the dCA in different postures. Using wavelet entropy, we estimated the statistical complexity of BFV for three postures. Repeated measures ANOVA showed that only the complexity of lay-sit had significant differences.