Novel cross-coupling reactions between organotellurides and Grignard reagents employing a MnCl2/CuI catalytic system

We present a general protocol for the cross-coupling reaction of Grignard reagents and organic tellurides. Aryl Grignard reagents react stereospecifically with vinyl tellurides in the presence of a catalytic amount of manganese (II) chloride and copper (I) iodide to produce good yields of the corresponding cross-coupling products. (C) 2012 Published by Elsevier Ltd.

Manganese-enhanced magnetic resonance imaging detects mossy fiber sprouting in the pilocarpine model of epilepsy

Purpose: Mossy fiber sprouting (MFS) is a frequent finding following status epilepticus (SE). The present study aimed to test the feasibility of using manganese-enhanced magnetic resonance imaging (MEMRI) to detect MFS in the chronic phase of the well-established pilocarpine (Pilo) rat model of temporal lobe epilepsy (TLE). Methods: To modulate MFS, cycloheximide (CHX), a protein synthesis inhibitor, was coadministered with Pilo in a subgroup of animals. In vivo MEMRI was performed 3 months after induction of SE and compared to the neo-Timm histologic labeling of zinc mossy fiber terminals in the dentate gyrus (DG). Key Findings: Chronically epileptic rats displaying MFS as detected by neo-Timm histology had a hyperintense MEMRI signal in the DG, whereas chronically epileptic animals that did not display MFS had minimal MEMRI signal enhancement compared to nonepileptic control animals. A strong correlation (r = 0.81, p < 0.001) was found between MEMRI signal enhancement and MFS. Significance: This study shows that MEMRI is an attractive noninvasive method for detection of mossy fiber sprouting in vivo and can be used as an evaluation tool in testing therapeutic approaches to manage chronic epilepsy.

Phase-disorder-induced firing activity in excitable neuronal networks with attractive and repulsive coupling

It has been revealed that the network of excitable neurons via attractive coupling can generate spikes under stimuli of subthreshold signals with disordered phases. In this paper, we explore the firing activity induced by phase disorder in excitable neuronal networks consisting of both attractive and repulsive coupling. By increasing the fraction of repulsive coupling, we find that, in the weak coupling strength case, the firing threshold of phase disorder is increased and the system response to subthreshold signals is decreased, indicating that the effect of inducing neuron firing by phase disorder is weakened with repulsive coupling. Interestingly, in the large coupling strength case, we see an opposite situation, where the coupled neurons show a rather large response to the subthreshold signals even with small phase disorder. The latter case implies that the effect of phase disorder is enhanced by repulsive coupling. A system of two-coupled excitable neurons is used to explain the role of repulsive coupling on phase-disorder-induced firing activity.

Hollow-fiber liquid-phase microextraction and gas chromatography-mass spectrometry of barbiturates in whole blood samples

Here, we present a method for measuring barbiturates (butalbital, secobarbital, pentobarbital, and phenobarbital) in whole blood samples. To accomplish these measurements, analytes were extracted by means of hollow-fiber liquid-phase microextraction in the three-phase mode. Hollow-fiber pores were filled with decanol, and a solution of sodium hydroxide (pH 13) was introduced into the lumen of the fiber (acceptor phase). The fiber was submersed in the acidified blood sample, and the system was subjected to an ultrasonic bath. After a 5 min extraction, the acceptor phase was withdrawn from the fiber and dried under a nitrogen stream. The residue was reconstituted with ethyl acetate and trimethylanilinium hydroxide. An aliquot of 1.0 mu L of this solution was injected into the gas chromatograph/mass spectrometer, with the derivatization reaction occurring in the hot injector port (flash methylation). The method proved to be simple and rapid, and only a small amount of organic solvent (decanol) was needed for extraction. The detection limit was 0.5 mu g/mL for all the analyzed barbiturates. The calibration curves were linear over the specified range (1.0 to 10.0 mu g/mL). This method was successfully applied to postmortem samples (heart blood and femoral blood) collected from three deceased persons previously exposed to barbiturates.

Contribution of the retrotrapezoid nucleus/parafacial respiratory region to the expiratory-sympathetic coupling in response to peripheral chemoreflex in rats

Moraes DJ, Dias MB, Cavalcanti-Kwiatkoski R, Machado BH, Zoccal DB. Contribution of retrotrapezoid nucleus/parafacial respiratory region to the expiratory-sympathetic coupling in response to peripheral chemoreflex in rats. J Neurophysiol 108: 882-890, 2012. First published May 16, 2012; doi:10.1152/jn.00193.2012.-Central mechanisms of coupling between respiratory and sympathetic systems are essential for the entrainment between the enhanced respiratory drive and sympathoexcitation in response to hypoxia. However, the brainstem nuclei and neuronal network involved in these respiratory-sympathetic interactions remain unclear. Here, we evaluated whether the increase in expiratory activity and expiratory-modulated sympathoexcitation produced by the peripheral chemoreflex activation involves the retrotrapezoid nucleus/parafacial respiratory region (RTN/pFRG). Using decerebrated arterially perfused in situ rat preparations (60-80 g), we recorded the activities of thoracic sympathetic (tSN), phrenic (PN), and abdominal nerves (AbN) as well as the extracellular activity of RTN/pFRG expiratory neurons, and reflex responses to chemoreflex activation were evaluated before and after inactivation of the RTN/pFRG region with muscimol (1 mM). In the RTN/pFRG, we identified late-expiratory (late-E) neurons (n = 5) that were silent at resting but fired coincidently with the emergence of late-E bursts in AbN after peripheral chemoreceptor activation. Bilateral muscimol microinjections into the RTN/pFRG region (n = 6) significantly reduced basal PN frequency, mean AbN activity, and the amplitude of respiratory modulation of tSN (P < 0.05). With respect to peripheral chemoreflex responses, muscimol microinjections in the RTN/pFRG enhanced the PN inspiratory response, abolished the evoked late-E activity of AbN, but did not alter either the magnitude or pattern of the tSN reflex response. These findings indicate that the RTN/pFRG region is critically involved in the processing of the active expiratory response but not of the expiratory-modulated sympathetic response to peripheral chemoreflex activation of rat in situ preparations.

Design of laminated piezocomposite shell transducers with arbitrary fiber orientation using topology optimization approach

Sensor and actuator based on laminated piezocomposite shells have shown increasing demand in the field of smart structures. The distribution of piezoelectric material within material layers affects the performance of these structures; therefore, its amount, shape, size, placement, and polarization should be simultaneously considered in an optimization problem. In addition, previous works suggest the concept of laminated piezocomposite structure that includes fiber-reinforced composite layer can increase the performance of these piezoelectric transducers; however, the design optimization of these devices has not been fully explored yet. Thus, this work aims the development of a methodology using topology optimization techniques for static design of laminated piezocomposite shell structures by considering the optimization of piezoelectric material and polarization distributions together with the optimization of the fiber angle of the composite orthotropic layers, which is free to assume different values along the same composite layer. The finite element model is based on the laminated piezoelectric shell theory, using the degenerate three-dimensional solid approach and first-order shell theory kinematics that accounts for the transverse shear deformation and rotary inertia effects. The topology optimization formulation is implemented by combining the piezoelectric material with penalization and polarization model and the discrete material optimization, where the design variables describe the amount of piezoelectric material and polarization sign at each finite element, with the fiber angles, respectively. Three different objective functions are formulated for the design of actuators, sensors, and energy harvesters. Results of laminated piezocomposite shell transducers are presented to illustrate the method. Copyright (C) 2012 John Wiley & Sons, Ltd.

Determination of the critical coupling of explosive synchronization transitions in scale-free networks by mean-field approximations

An explosive synchronization can be observed in scale-free networks when Kuramoto oscillators have natural frequencies equal to their number of connections. The present paper reports on mean-field approximations to determine the critical coupling of such explosive synchronization. It has been verified that the equation obtained for the critical coupling has an inverse dependence on the network average degree. This expression differs from those whose frequency distributions are unimodal and even. In this case, the critical coupling depends on the ratio between the first and second statistical moments of the degree distribution. Numerical simulations were also conducted to verify our analytical results.

Signal amplification of active rotators with phase-shifted coupling

In this paper, we study the signal amplification of coupled active rotators with phase-shifted coupling. We find that the system's response to the external subthreshold signal can be significantly affected by each of the two types of phase-shifted couplings: identical and non-identical phase-shifted couplings. Moreover, through both theoretical analysis and numerical simulations, we have figured out the optimal phase shift, at which the largest signal amplification is generated. These results show that the phase-shifted coupling plays an important role in regulating the system's response to the subthreshold signal.

Using Equivalent Emission Sources to Evaluate the Coupling Between Components

The electromagnetic interference between the electronic systems or their components influences the performance of the systems. For that reason, it is important to model these interferences in order to optimize the position of the systems or their components. In this paper, a method is proposed to construct the equivalent emission source models of systems. The proposed method is based on the multipolar expansion by representing the radiated emission of generic structures in a spherical reference (r, theta, phi). Some results are presented illustrating our method.

Temperature Sensing Using Colloidal-Core Photonic Crystal Fiber

We report on a temperature sensor based on the monitoring of the luminescence spectrum of CdSe/ZnS nanocrystals, dispersed in mineral oil and inserted into the core of a photonic crystal fiber. The high overlap between the pump light and the nanocrystals as well as the luminescence guiding provided by the fiber geometry resulted in relatively high luminescence powers and improved optical signal-to-noise ratio (OSNR). Also, both core end interfaces were sealed so as to generate a more stable and robust waveguide structure. Temperature sensitivity experiments indicated a 70 pm/degrees C spectral shift over the 5 degrees C to 90 degrees C range.

Push-out bond strengths of different dental cements used to cement glass fiber posts

Statement of problem: Since the introduction of glass fiber posts, irreversible vertical root fractures have become a rare occurrence; however, adhesive failure has become the primary failure mode. Purpose: The purpose of this study was to evaluate the push-out bond strength of glass fiber posts cemented with different luting agents on 3 segments of the root. Material and methods: Eighty human maxillary canines with similar root lengths were randomly divided into 8 groups (n=10) according to the cement assessed (Rely X luting, Luting and Lining, Ketac Cem, Rely X ARC, Biscem, Duo-link, Rely X U100, and Variolink II). After standardized post space preparation, the root dentin was pretreated for dualpolymerizing resin cements and untreated for the other cements. The mixed luting cement paste was inserted into post spaces with a spiral file and applied to the post surface that was seated into the canal. After 7 days, the teeth were sectioned perpendicular to their long axis into 1-mm-thick sections. The push-out test was performed at a speed of 0.5 mm/min until extrusion of the post occurred. The results were evaluated by 2-way ANOVA and the all pairwise multiple comparison procedures (Tukey test) (?=.05). Results: ANOVA showed that the type of interaction between cement and root location significantly influenced the push-out strength (P<.05). The highest push-out strength results with root location were obtained with Luting and Lining (S3) (19.5 ±4.9 MPa), Ketac Cem (S2) (18.6 ±5.5 MPa), and Luting and Lining (S1) (18.0 ±7.6 MPa). The lowest mean values were recorded with Variolink II (S1) (4.6 ±4.0 MPa), Variolink II (S2) (1.6 ±1.5 MPa), and Rely X ARC (S3) (0.9 ±1.1 MPa). Conclusions: Self-adhesive cements and glass ionomer cements showed significantly higher values compared to dual-polymerizing resin cements. In all root segments, dual-polymerizing resin cements provided significantly lower bond strength. Significant differences among root segments were found only for Duo-link cement.

Ultra-structural mapping of sugarcane bagasse after oxalic acid fiber expansion (OAFEX) and ethanol production by Candida shehatae and Saccharomyces cerevisiae

Background Diminishing supplies of fossil fuels and oil spills are rousing to explore the alternative sources of energy that can be produced from non-food/feed-based substrates. Due to its abundance, sugarcane bagasse (SB) could be a model substrate for the second-generation biofuel cellulosic ethanol. However, the efficient bioconversion of SB remains a challenge for the commercial production of cellulosic ethanol. We hypothesized that oxalic-acid-mediated thermochemical pretreatment (OAFEX) would overcome the native recalcitrance of SB by enhancing the cellulase amenability toward the embedded cellulosic microfibrils. Results OAFEX treatment revealed the solubilization of hemicellulose releasing sugars (12.56 g/l xylose and 1.85 g/l glucose), leaving cellulignin in an accessible form for enzymatic hydrolysis. The highest hydrolytic efficiency (66.51%) of cellulignin was achieved by enzymatic hydrolysis (Celluclast 1.5 L and Novozym 188). The ultrastructure characterization of SB using scanning electron microscopy (SEM), atomic force microscopy (AFM), Raman spectroscopy, Fourier transform–near infrared spectroscopy (FT-NIR), Fourier transform infrared spectroscopy (FTIR), and X-ray diffraction (XRD) revealed structural differences before and after OAFEX treatment with enzymatic hydrolysis. Furthermore, fermentation mediated by C. shehatae UFMG HM52.2 and S. cerevisiae 174 showed fuel ethanol production from detoxified acid (3.2 g/l, yield 0.353 g/g; 0.52 g/l, yield, 0.246 g/g) and enzymatic hydrolysates (4.83 g/l, yield, 0.28 g/g; 6.6 g/l, yield 0.46 g/g). Conclusions OAFEX treatment revealed marked hemicellulose degradation, improving the cellulases’ ability to access the cellulignin and release fermentable sugars from the pretreated substrate. The ultrastructure of SB after OAFEX and enzymatic hydrolysis of cellulignin established thorough insights at the molecular level.

Functional coupling of sensorimotor and associative areas during a catching ball task: a qEEG coherence study

Abstract Background Catching an object is a complex movement that involves not only programming but also effective motor coordination. Such behavior is related to the activation and recruitment of cortical regions that participates in the sensorimotor integration process. This study aimed to elucidate the cortical mechanisms involved in anticipatory actions when performing a task of catching an object in free fall. Methods Quantitative electroencephalography (qEEG) was recorded using a 20-channel EEG system in 20 healthy right-handed participants performed the catching ball task. We used the EEG coherence analysis to investigate subdivisions of alpha (8-12 Hz) and beta (12-30 Hz) bands, which are related to cognitive processing and sensory-motor integration. Results Notwithstanding, we found the main effects for the factor block; for alpha-1, coherence decreased from the first to sixth block, and the opposite effect occurred for alpha-2 and beta-2, with coherence increasing along the blocks. Conclusion It was concluded that to perform successfully our task, which involved anticipatory processes (i.e. feedback mechanisms), subjects exhibited a great involvement of sensory-motor and associative areas, possibly due to organization of information to process visuospatial parameters and further catch the falling object.

Caffeine determination at a carbon fiber ultramicroelectrodes by fast-scan cyclic voltammetry

Caffeine determination using a fast-scan voltammetric procedure at a carbon fiber ultramicroelectrode (CF-UME) is described. The CF-UME was submitted to electrochemical pretreatment. Parameters such as number of acquisition cycles, scan rate, potential window, and the electrochemical surface pretreatment were optimized. Using the optimized conditions, it was possible to achieve a LDR from 10.0 up to 200 μmol L-1, with a LOD of 3.33 μmol L-1. The method has been applied in the determination of caffeine in commercial samples, with errors of 1.0-3.5% in relation to the label values and recoveries of 97-114% within the linear range.

Assessment of cumulative damage by using ultrasonic C-scan on carbon fiber/epoxy composites under thermal cycling

In recent years, structural composites manufactured by carbon fiber/epoxy laminates have been employed in large scale in aircraft industries. These structures require high strength under severe temperature changes of -56° until 80 °C. Regarding this scenario, the aim of this research was to reproduce thermal stress in the laminate plate developed by temperature changes and tracking possible cumulative damages on the laminate using ultrasonic C-scan inspection. The evaluation was based on attenuation signals and the C-scan map of the composite plate. The carbon fiber/epoxy plain weave laminate underwent temperatures of -60° to 80 °C, kept during 10 minutes and repeated for 1000, 2000, 3000 and 4000 times. After 1000 cycles, the specimens were inspected by C-scanning. A few changes in the laminate were observed using the inspection methodology only in specimens cycled 3000 times, or so. According to the found results, the used temperature range did not present enough conditions to cumulative damage in this type of laminate, which is in agreement with the macro - and micromechanical theory.