Palladium(II) complexes bearing the new pincer ligand 3,5-bis(indazol-2-ylmethyl)toluene; synthesis and catalytic properties

The reaction of 3,5-bis(bromomethyl)toluene with 1H-indazole in toluene, in the presence of triethylamine, yields the ligand 3,5-bis(indazol-2-ylmethyl)toluene (1). Compound 1 reacts with Pd(OAc)₂ in refluxing acetic acid, followed by a metathetic reaction with lithium chloride and with [PdCl₂(cod)] (cod = 1,5-cyclooctadiene) in refluxing acetonitrile to give the complexes [PdCl{3,5-bis(indazol-2-ylmethyl)tolyl-N,C,N}] (2) and [PdCl₂{3,5-bis(indazol-2-ylmethyl)toluene-N,N}] (3), respectively. Compounds 1–3 were characterized by elemental analyses, mass spectra and IR and NMR (¹H, ¹³C) spectroscopies. The molecular structure of 1 was also determined by single-crystal X-ray diffraction. The palladium(II) complexes (2,3) were tested as catalysts in ethylene polymerization and in C–C coupling reactions involving aryl halides substrates.     

Identification of phases and precipitates by AFM in duplex stainless steel unions

ABSTRACT

Atomic Force Microscopy (AFM), a characterization technique that generates topographic images of surfaces at very high resolutions, works by recording the surface relief details of the material with a cantilever which moves over the sample, while a piezoelectric sensor monitors changes in height. This technique is useful for identifying phases, particles and precipitates on a nanoscale and is therefore proposed for identifying them in the fusion zone of welded components and for early identification of faults due to cracking. This is a technique that does not require conductive samples, or special metallographic preparation of specimens as is the case with electron microscopy. The material studied is a duplex 2205 stainless steel, welded by means of gas tungsten arc welding (GTAW). The welded material was subjected to stress tests. The test specimens were characterized using optical microscopy, scanning electron microscopy, atomic force microscopy and nanoindentation tests. The results focus on the identification of the specific magnetic, topographic and hardness characteristics of each of the phases, particles and areas present in the base metal, the fusion zone and the zone deformed by the fracture.     

Relationship between vegetation of the levee neo‐ecosystems and environmental heterogeneity in the Lower Delta of the Paraná River,Argentina

The relationship between environmental heterogeneity and the vegetation of the levee neo‐ecosystems in the Delta of the Paraná River was studied. These habitat types were considered plant communities of recent origin related to local productive activities. Vegetation coverage was evaluated in 97 plots of three different environmental units (A, B and C), using classification analysis, indirect and direct ordinations. The differential vegetation in different environmental units could be related to a greater fluvial influence of the Paraná River on unit A and a greater tidal influence of the de la Plata River on units B and C. The Lower Delta hydrological regimes only affect a few of edaphic variables particularly pH, organic matter percentage and clay content. To understand the spatial pattern of neo‐ecosystems vegetation, it is also necessary to consider the invasion of alien species that has been taking place for over 50 years.     

Inhibitory effect of Escherichia coli endotoxin on skeletal muscle contractility

OBJECTIVE: Endotoxemia in rabbits is associated with decreases in oxygen transport, tissue hypoxia, metabolic acidosis, and impaired oxygen extraction. In this study, we tested the hypothesis that endotoxin also inhibits skeletal muscle contractility directly. DESIGN: Randomized animal study. SETTING: Accredited animal research facility. SUBJECTS: New Zealand white rabbits of either sex, weighing 2.55 +/- 0.20 kg. INTERVENTIONS: We compared two groups of rabbits (n = 10 each) undergoing continuous electrical stimulation of the left hindlimb (maximal isometric twitch contraction at 0.25 Hz). One group (septic) was given an intravenous infusion of Escherichia coli endotoxin. The control group was subjected to decreases in cardiac output by inflating a balloon placed in the right ventricle. MEASUREMENTS AND MAIN RESULTS: Endotoxin or balloon inflation resulted in comparable decreases in cardiac output (49% and 53%, respectively). Hindlimb oxygen transport decreased to similar values for both groups (4.9 +/- 0.3 and 4.2 +/- 0.5 mL/min/kg, respectively). Systemic oxygen extraction ratio was greater in the control group (0.72 +/- 0.03) than in the septic group (0.55 +/- 0.04; p < .05). There were no differences in hindlimb oxygen extraction ratio. Decreases in hindlimb forces were greater in the septic group (42 +/- 4%) than in the control group (18 +/- 3%, p < .01). Force frequency curves obtained at the beginning and the end of the experiment showed greater fatigue in the septic group. CONCLUSIONS: The intravenous infusion of Escherichia coli endotoxin produces a direct inhibitory effect on skeletal muscle contractility in rabbits. This phenomenon is independent of decreases in oxygen transport and blood pH. Our data support the notion of a direct cellular effect of endotoxin, or of an associated cytokine, on skeletal muscle contractility. The mechanism responsible for this phenomenon is unknown.     

Macroporous silicon for high-capacitance devices using metal electrodes

In this paper, high-capacity energy storage devices based on macroporous silicon are demonstrated. Small footprint devices with large specific capacitances up to 100 nF/mm², and an absolute capacitance above 15 μF, have been successfully fabricated using standard microelectronics and MEMS techniques. The fabricated devices are suitable for high-density system integration. The use of 3-D silicon structures allows achieving a large surface to volume ratio. The macroporous silicon structures are fabricated by electrochemical etching of silicon. This technique allows creating large structures of tubes with either straight or modulated radial profiles in depth. Furthermore, a very large aspect ratio is possible with this fabrication method. Macroporous silicon grown this way permits well-controlled structure definition with excellent repeatability and surface quality. Additionally, structure geometry can be accurately controlled to meet designer specifications. Macroporous silicon is used as one of the electrodes over which a silicon dioxide insulating layer is grown. Several insulator thicknesses have been tested. The second capacitor electrode is a solid nickel filling of the pores prepared by electroplating in a low-temperature industry standard process. The use of high-conductivity materials allows reaching small equivalent series resistance near 1 Ω. Thanks to these improvements, the presented devices are capable of operating up to 10 kHz.

PACS

84.32.Tt; 81.15.Pq; 81.05.Rm     

MaxPHOS Ligand: PH/NH Tautomerism and Rhodium‐ Catalyzed Asymmetric Hydrogenations

MaxPHOS is an active and robust P‐stereogenic ligand for asymmetric catalysis. The presence of an  NH bridge between the two phosphine moieties allows the NH/PH tautomerism to take place. The neutral ligand, in which the NH form predominates, is an air‐sensitive compound. However, protonation of MaxPHOS leads to the stable PH form of the ligand, in which the overall positive charge is distributed on both P centers. This protonation turns the MaxPHOS⋅HBF₄ salt 3 into an air‐stable compound both in the solid state and in solution. The salt 3 is also a convenient precursor for the preparation of rhodium(I) complexes by direct ligand exchange with the complex [Rh(acac)(cod)]. Finally, the corresponding rhodium(I)‐MaxPHOS complex was tested in the asymmetric hydrogenation of a wide range of substrates. The complex proved to be a highly selective and robust system in these reactions.

     

Spin-wave interference patterns created by spin-torque nano-oscillators for memory and computation

Magnetization dynamics in nanomagnets has attracted broad interest since it was predicted that a dc current flowing through a thin magnetic layer can create spin-wave excitations. These excitations are due to spin momentum transfer, a transfer of spin angular momentum between conduction electrons and the background magnetization, that enables new types of information processing. Here we show how arrays of spin-torque nano-oscillators can create propagating spin-wave interference patterns of use for memory and computation. Memristic transponders distributed on the thin film respond to threshold tunnel magnetoresistance values, thereby allowing spin-wave detection and creating new excitation patterns. We show how groups of transponders create resonant (reverberating) spin-wave interference patterns that may be used for polychronous wave computation and information storage.     

A survey on geometrical reconstruction as a core technology to sketch-based modeling

In this work, the background and evolution of three-dimensional reconstruction of line drawings during the last 30 years is discussed. A new general taxonomy is proposed to make apparent and discuss the historical evolution of geometrical reconstruction and their challenges. The evolution of geometrical reconstruction from recovering know-how stored in engineering drawings to sketch-based modeling for helping in the first steps of conceptual design purposes, and the current challenges of geometrical reconstruction are discussed too.     

Longitudinal trends and gender differences in physical fitness and lifestyle factors in career U.S. Navy personnel (1983-1994)

This study examines long-term health and physical readiness trends in the U.S. Navy. We mailed lifestyle questionnaires to all participants in baseline studies between 1983 and 1989 who were still on active duty in 1994. Commands provided body composition and physical readiness test scores for the participants. Two longitudinal cohorts were created: an 8-year sample (N = 640) with matched data from 1986, 1989, and 1994; and an 11-year sample (N = 1,576), with data from 1983 and 1994. Analyses of both cohorts revealed significant improvements in cardiovascular fitness, muscle strength, exercise, lean body mass, dietary habits, and sleep, as well as significant decreases in tobacco and alcohol use and job stress. However, hypertension rates, percentage of body fat, and body mass index increased over time. Women's scores were significantly better than men's on a number of factors. Overall, these findings suggest that the Navy's health promotion efforts have had a significant positive effect on the fitness and health behaviors of career Navy men and women.