Graphite Oxide and Aromatic Amines: Size Matters

Experimental and theoretical studies are performed in order to illuminate, for first time, the intercalation mechanism of polycyclic aromatic molecules into graphite oxide. Two representative molecules of this family, aniline and naphthalene amine are investigated. After intercalation, aniline molecules prefer to covalently connect to the graphene oxide matrix via chemical grafting, while napthalene amine molecules bind with the graphene oxide surface through π–π interactions. The presence of intercalated aromatic molecules between the graphene oxide layers is demonstrated by X‐ray diffraction, while the type of interaction between graphene oxide and polycyclic organic molecules is elucidated by X‐ray photoelectron spectroscopy. Combined quantum mechanical and molecular mechanical calculations describe the intercalation mechanism and the aniline grafting, rationalizing the experimental data. The present work opens new perspectives for the interaction of various aromatic molecules with graphite oxide and the so‐called “intercalation chemistry”.     

The Density of States and the Pertinent Electronic Properties of the Quasi 2DEG in Simple and DMS Structures Subjected to an In-Plane Magnetic Field

We analyze the important changes induced to the density of states (DOS) of a quasi two-dimensional-electron-gas (2DEG), when it is subjected to an in-plane magnetic field, B. The DOS diverges significantly from the famous step-like form and this introduces changes to the pertinent electronic properties. In order to calculate the DOS it is indispensable to use a self-consistent approach. The eigenvalue problem has to be solved for each subband index i and in-plane wavevector, k _x, when the quasi 2DEG is parallel to the xy-plane and B is applied along the y-axis. Although the modification of the DOS is usually ignored, we show here that not only the general shape of the DOS varies, but this effect is also quantitative.     

Design of responsive double-hydrophilic A-b-(B-co-C) diblock terpolymers with tunable thermosensitivity

Double-hydrophilic poly[(oligo(ethylene glycol) methacrylate)-co-methyl methacrylate]-b-poly(2-(diethylamino)ethyl methacrylate), P(EGMA-co-MMA)-b-PDEA, diblock terpolymers were designed and explored in aqueous media. Thanks to the thermosensitivity of the P(EGMA-co-MMA) statistical block and the pH sensitivity of the PDEA block, these terpolymers form two distinct micellar self-assemblies at different conditions of pH and temperature. The thermosensitivity of these terpolymers can be tuned by controlling the LCST of the statistical block through its monomer unit composition.     

Mechanistic aspects of the water–gas shift reaction on alumina-supported noble metal catalysts: In situ DRIFTS and SSITKA-mass spectrometry studies

Steady-state isotopic transient kinetic analysis (SSITKA) experiments coupled with mass spectrometry were performed for the first time to study essential mechanistic aspects of the water–gas shift (WGS) reaction over alumina-supported Pt, Pd, and Rh catalysts. In particular, the concentrations (μmol g⁻¹) of active intermediate species found in the carbon-path from CO to the CO₂ product gas (use of ¹³CO), and in the hydrogen-path from H₂O to the H₂ product gas (use of D₂O) of the reaction mechanism were determined. It was found that by increasing the reaction temperature from 350 to 500 °C the concentration of active species in both the carbon-path and hydrogen-path increased significantly. Based on the large concentration of active species present in the hydrogen-path (OH/H located on the alumina support), the latter being larger than six equivalent monolayers based on the exposed noble metal surface area (θ > 6.0), the small concentration of OH groups along the periphery of metal-support interface, and the significantly smaller concentration (μmol g⁻¹) of active species present in the carbon-path (adsorbed CO on the noble metal and COOH species on the alumina support and/or the metal-support interface), it might be suggested that diffusion of OH/H species on the alumina support towards catalytic sites present in the hydrogen-path of reaction mechanism might be considered as a slow reaction step. The formation of labile OH/H species is the result of dissociative chemisorption of water on the alumina support, where the role of noble metal is to activate the CO chemisorption and likely to promote formate decomposition into CO₂ and H₂ products. It was found that there is a good correlation between the surface concentration and binding energy of CO on the noble metal (Pt, Pd or Rh) with the activity of alumina-supported noble metal towards the WGS reaction.     

Transition phenomena of polymers in mixed solvents in the vicinity of theta conditions: Effect of preferential adsorption

Viscosimetric measurements were obtained with the ternary systems polystyrene/dioxane/methanol, polystyrene/benzene/methanol and poly(methyl methacrylate)/dioxane/cyclohexane, changing the solvent mixture composition at constant temperature. The polystyrene and poly(methyl methacrylate) systems exhibit a transition phenomenon with solvent-mixture composition in which the polymer is just above the theta condition. In the case where two theta conditions occur ((θ-intra, θ-inter) the transition point is closely related to the intramolecular theta conditions. Moreover the intramolecular theta conditions vary with the molecular weight in the region of molecular weights where the preferential adsorption also varies. This variation induces a variation of the transition point with molecular weight which obeys a formula analogous to that giving the variation of the preferential adsorption with molecular weight.     

Viscometric determination of the molecular weight of polymers in the low molecular weight region

In order to overcome the difficulty of the determination of the molecular weight of a polymer in the low molecular weight region by viscometry using the Mark–Houwink–Sakurada (MHS) equation, we have proposed the Dondos–Benoit relationship [η]^?1 = A₂ + AM^?1/2, for a number of polymer–solvent systems, for which we give the numerical values of the parameters A₁ and A₂. Furthermore, we suggest a method for the determination of the above parameters using the MHS constants a and k.     

Rheological behaviour of multiphase slurries for combustion applications

The rheological behaviour of a concentrated coal-water-fuel oil slurry was investigated with a tube viscometer, to optimize its formulation. The non-Newtonian character of the slurry follows the rheological model of Ostwald de Waele, according to the experimental results obtained. A factorial plan was used and empirical equations were obtained which correlate rheological characteristics with the mass fractions of the slurry components.     

Accelerated collection of sensor data by mobility-enabled topology ranks

We study the problem of fast and energy-efficient data collection of sensory data using a mobile sink, in wireless sensor networks in which both the sensors and the sink move. Motivated by relevant applications, we focus on dynamic sensory mobility and heterogeneous sensor placement. Our approach basically suggests to exploit the sensor motion to adaptively propagate information based on local conditions (such as high placement concentrations), so that the sink gradually “learns” the network and accordingly optimizes its motion. Compared to relevant solutions in the state of the art (such as the blind random walk, biased walks, and even optimized deterministic sink mobility), our method significantly reduces latency (the improvement ranges from 40% for uniform placements, to 800% for heterogeneous ones), while also improving the success rate and keeping the energy dissipation at very satisfactory levels.