Pincer Type Ditertiary Aminomethylphosphine–Pd(II) Complexes Supported on Multi-Walled Carbon Nanotube: Catalytic Properties in Heck C–C Coupling Reactions

Pincer type aminomethylphosphine–Pd(II) complexes supported on multi-walled carbon nanotube (MWCNT) have been synthesized and characterized using X-Ray diffraction spectrometry, scanning electron microscopy, thermal analysis, energy dispersive X-Ray, Fourier transform infrared spectrometry, transmission electron microscopy (TEM) and ultraviolet–visible spectrometry techniques. The novel complexes were tried as catalysts in Heck C–C coupling reactions. The crystallite size and lattice strain of the MWCNT based compounds were calculated by the Scherrer’s equation. The optical parameters of the MWCNT based structures were analyzed and the band gap enhanced from 4.42 to 4.98 eV. Different solvents (toluene, 1,4-diooxane, DMF and NMP) and bases (Et₃N, Na₂CO₃, NaOAc and K₂CO₃) were tried at different temperatures (80, 100 and 110 °C) in the cross-coupling of bromobenzene with styrene. The optimum yield was found in the presence of K₂CO₃, 110 °C in 1,4-dioxane solvent system.     

Addition of tetrachloromethane to alkenes catalyzed by cobalt(II)-amine complex

The cobalt(II)-2-methylpropylamine complex is an efficient catalyst for addition of tetrachloromethane to alkenes under mild reaction conditions (80 °C) providing 1 1 adducts up to 99.5% yield. Reactions with vinyl monomers provided low yield of 1 1 addition products (5–48%) presumably due to radical chain processes favoring telomerization and polymerization.     

The effect of 2D and 3D visual modes on surgical task performance: role of expertise and adaptation processes

The aim of this paper is to analyze how novices and experts are able to safely adapt and transfer their skills to new technology in medical domain. In order to answer this question, we compared the performance of 12 novices (medical students) with the performance of 12 laparoscopic surgeons (using a 2D view) and 4 robotic surgeons, using a new robotic system that allows 2D and 3D view. Our results showed a trivial effect of expertise (surgeons generally performed better than novices). Moreover, they revealed that experts have adaptive transfer capacities and are able to transfer their skills independently of the human–machine system. However, even if we observe transfer of skills, we showed that expert’s performance may be disturbed by changes in their usual environment. In a safety perspective but also for novice and expert training, this study emphasizes the necessity to take into account the impact of these environmental changes and the expert’s adaptive capacities but also the limits of expert’s adaptive capacities.     

Fetal phonocardiography--past and future possibilities

The paper presents an overview of the 15 year long development of fetal phonocardiography including the works on the applied signal processing methods for identification of sound components. Based on the improvements achieved on this field, the paper shows that beyond the traditional CTG test the phonocardiography may be successfully applied for long-term fetal measurements and home monitoring. In addition, by indication of heart murmurs based on a comprehensive analysis of the recorded heart sound congenital heart defects can also be detected together with additional features in the third trimester. This makes an early widespread screening possible combined with the prescribed CTG test even at home using a telemedicine system.     

Dynamic clothing insulation. Measurements with a thermal manikin operating under the thermal comfort regulation mode

The main objective of the present work is the assessment of the thermal insulation of clothing ensembles, both in static conditions and considering the effect of body movements. The different equations used to calculate the equivalent thermal resistance of the whole body, namely the serial, the global and the parallel methods, are considered and the results are presented and discussed for the basic, the effective and the total clothing insulations. The results show that the dynamic thermal insulation values are always lower than the corresponding static ones. The highest mean relative difference [(static-dynamic)/static] was obtained with the parallel method and the lowest with the serial. For I_cl the mean relative differences varied from 0.5 to 13.4% with the serial method, from 5.6 to 14.6% with the global and from 7.2 to 17.7% with the parallel method. In addition, the dynamic tests presents the higher mean relative differences between the calculation methods. The results also show that the serial method always presents the higher values and the parallel method the lowest ones. The relative differences between the calculation methods {[(serial-global)/global] and [(parallel-global)/global]} were sometimes significant and associated to the non-uniform distribution of the clothing insulation. In fact, the ensembles with the highest thermal insulation values present the highest differences between the calculation methods.     

Direction Kernels: using a simplified 3D model representation for grasping

Humans decide how to carry out a spontaneous interaction with an object by using the whole geometric information obtained from their eyes. The aim of this paper is to present how our object representation model MWS (Adán in Comput Vis Image Underst 79:281–307, 2000) can help a robot manipulator to make a single and reliable interaction. The contribution of this paper is particularly focused on the grasp synthesis stage. The main idea is that the grasping system, through MWS, can use non-strict-local features of the contact points to find a consistent grasping configuration. The Direction Kernels (DK) concept, which is integrated into the MWS model, is used to define a set of candidate contact-points and interaction regions. The set of DK is a global feature which represents the principal normal vectors of the object and their relative weight in a three-connectivity mesh model. Our method calculates the optimal grasp points (which are ordered according to the quality function) for two-finger grippers, whilst maintaining the requirements of force closure and safety of the grasp. Our strategy has been extensively tested on real free-shape objects using a 6 DOF industrial robot.     

Wave and Flow Response to an Artificial Surf Reef: Laboratory Measurements

Waves and currents are essential elements in the design of an artificial surfing reef (ASR). ASRs are primarily designed to optimize the surfing conditions (i.e., increase the surfability of the incoming waves) possibly in combination with the shoreline protection from erosion. The currents generated by waves breaking on the ASR play an important role in the surfability through the wave-current interaction (WCI). Depending on the design, the WCI may negatively affect the surfability by causing the waves to break prematurely due to the current-induced wave steepening. In addition, wave breaking tends to become more irregular due to the temporal variability of the underlying currents. To mitigate the negative effects of wave breaking induced currents on the surfability, three ASR layouts are examined through detailed laboratory experiments. The layouts differ in the alongshore separation distance between two symmetrical reef sides. The ensuing flow circulations are examined in detail with both in situ current meters and video observations of surface drifters. This is done for regular incident waves, bichromatic incident waves, and irregular incident waves, all with equal energy. A data analysis shows that for a given layout the mean flow patterns for regular, bichromatic, and irregular waves are qualitatively similar, with oblique rip currents exiting at either side of the reef and strong flow circulations onshore of the gap in between the two reef sides. Increasing the separation distance leads to a significant reduction of the obliquely exiting rip currents at the outer sides of the reef, but an increase in the flow circulation onshore of the gap. This has a positive effect on the surfability by reducing the negative effects associated with the WCI on the wave breaking, thus, providing longer rides.     

Characterization of biodegradable semi‐interpenetrating polymer based on poly(vinyl alcohol) and sodium alginate containing natural neem (Azadirachta indica) for controlled release application

A biodegradable novel semi‐interpenetrating polymer network based on poly(vinyl alcohol) (PVA) and sodium alginate containing neem (Azadirachta indica) in the presence of azadirachtin‐A (neem Aza‐A) as well as glutaraldehyde as a crosslinking agent was prepared for use in the controlled released of neem Aza‐A. This is necessary because neem Aza‐A is not stable in the environment. The neem Aza‐A‐containing beads were prepared using various experimental parameters, such as the extent of crosslinking and the amount of loading, in order to optimize the process variables. The chemical structure of the capsule wall was evaluated through X‐ray diffraction. In addition, the swelling behaviour of the capsules and their thermal stability were investigated. The strength of the capsule wall depended on the PVA in the matrix and the crosslinking density. Scanning electron microscopy, electron probe microanalysis and atomic force microscopy data indicated that the structure of the bead walls is rough and nonporous. Swelling results indicated that swelling of the polymeric beads decreases with increasing exposure time to the crosslinking agent. At particular intervals, the remaining concentration of neem Aza‐A was analysed using high‐performance liquid chromatography. The release data were fitted to an empirical equation to estimate the kinetic parameters. The degree of release of neem Aza‐A was controlled by the parameter conditions. Copyright © 2010 Society of Chemical Industry     

Polyol synthesis of reduced graphene oxide supported platinum electrocatalysts for fuel cells: Effect of Pt precursor,support oxidation level and pH

In this work, a comprehensive study on the polyol synthesis of platinum supported on reduced graphene oxide (Pt/rGO) catalysts, including both ex-situ and in-situ characterizations of the prepared Pt/rGO catalysts, was performed. The polyol synthesis was studied considering the influence of the platinum precursor, oxidation level of graphite oxide and pH of reaction medium. The as-prepared catalysts were analyzed using thermo-gravimetric (TG) analysis, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and cyclic voltammetry (CV). The best results in terms of platinum particle size and distribution were obtained when the synthesis was performed in acidic medium, using chloroplatinic acid as precursor and using graphene oxide with high oxidation level. The most promising graphene-supported catalyst was used to prepare a polymer electrolyte membrane fuel cell electrode. The membrane electrode assembly (MEA) prepared with graphene-based electrode was compared with a MEA prepared with catalyst based on commercial platinum supported in carbon black (Pt/C). Single cell characterization included polarization curves and in-situ electrochemical impedance spectroscopy (EIS). The graphene-based electrode presented promising albeit unstable electrochemical performance due to water management issues. Additionally, EIS measurements revealed that the MEA made with Pt/rGO catalyst presented a lower mass transport resistance than the commercial Pt/C.     

Polymer heterogeneity in waterborne coatings

An overview is presented of the progress in understanding polymer heterogeneity over the last 20 years and how this has contributed to the improvement of coatings. Solvent-based polymers are homogeneous in nature, since all polymeric materials tend to be dissolved in the same solvent mixture. This is different for most waterborne polymers, which tend to be present in a compartmentalized way. Most polymeric materials are present in particles, which are separated by the continuous aqueous phase. This gives excellent opportunities to create particle morphologies that form the basis for the film morphology after drying of the coating. This article gives an overview of the various types of heterogeneity which are accessible in waterborne polymers and will show how heterogeneity in the polymer can contribute to the solution of several persistent problems of the coating industry.