Homogenization of the inviscid incompressible fluid flow through a 2D porous medium

We consider the non-stationary incompressible Euler equations in a 2D porous medium. We suppose a periodic porous medium, with the period proportional to the characteristic pore size and with connected fluid part. The flow is subject to an external force, corresponding to an inflow. We start from an initial irrotational velocity and prove that the effective filtration velocity satisfies a transient filtration law. It has similarities with Darcy's law, but it now connects the time derivative of the filtration velocity with the pressure gradient. The viscosity does not appear in the filtration law any more and the permeability tensor is determined through auxiliary problems of decomposition type. Using the limit problem, we construct the correction for the fluid velocity and prove that -norm of the error is of order . Similarly, we estimate the difference between the fluid pressure and its correction in as .

     

Enhanced Controllability of Low Reynolds Number Swimmers in the Presence of a Wall

Swimming, i.e., being able to advance in the absence of external forces by performing cyclic shape changes, is particularly demanding at low Reynolds numbers which is the regime of interest for micro-organisms and micro-robots. We focus on self-propelled stokesian robots composed of assemblies of balls and we prove that the presence of a wall has an effect on their motility. To rest on what has been done in Alouges et al. (Discrete Contin. Dyn. Syst., Ser. B 18(5):1189–1215, 2013) for such systems swimming on R ³, we demonstrate that a controllable swimmer remains controllable in a half space whereas the reachable set of a non fully controllable one is increased by the presence of a wall.     

Carbon Corrosion in Proton-Exchange Membrane Fuel Cells: Spectrometric Evidence for Pt-Catalysed Decarboxylation at Anode-Relevant Potentials

The carbon oxidation reaction (COR) is a critical issue in proton-exchange membrane fuel cells (PEMFCs), as carbon in various forms is the most used electrocatalyst support material. The COR is thermodynamically possible above the C/CO₂ standard potential, but its rate becomes significantly important only at high overpotential (e. g. PEMFC cathode potential). Herein, using on-line differential electrochemical mass spectrometry, we show that oxygen-containing carbon surface groups present on high-surface aera carbon, Vulcan XC72 or reinforced graphite are oxidized at PEMFC anode-relevant potential (E=0.1 V vs. the reversible hydrogen electrode, RHE), but not at E=0.4 V vs. RHE. We rationalized our findings by considering a Pt-catalysed decarboxylation mechanism in which Pt nanoparticles provide adsorbed hydrogen species to the oxygen-containing carbon surface groups, eventually leading to evolution of carbon dioxide and carbon monoxide. These results shed fundamental light on an unexpected degradation mechanism and facilitate the understanding of the long-term stability of PEMFC anode nanocatalysts.     

Preparation of Well‐Defined Poly[(ethylene oxide)‐block‐(sodium 2‐acrylamido‐2‐methyl‐1‐propane sulfonate)] Diblock Copolymers by Water‐Based Atom Transfer Radical Polymerization

Summary: Well‐defined poly[(ethylene oxide)‐block‐(sodium 2‐acrylamido‐2‐methyl‐1‐propane sulfonate)] diblock copolymers [P(EO_m‐b‐AMPS_n)], have been obtained by water‐based ATRP using α‐methoxy‐ω‐(2‐methylbromoisobutyrate) poly(ethylene oxide)s (MeO‐P[EO]_m‐BrⁱB with m ranging from 12 to 113) and CuBr · 2Bpy (Bpy for 2,2′‐bipyridyl) as macroinitiator and catalytic complex, respectively. Compared to direct polymerization in water, it has been demonstrated that the water/methanol (3:1, v/v) mixture is better suited for predicting the final number‐average molar mass from the initial monomer‐to‐macroinitiator molar ratio and achieving a quite narrow polydispersity, even at high monomer conversion ( ≈ 1.4 at 80% conversion). The effect of temperature, solvent mixture composition and addition of NaCl salt on the polymerization rate and extent of control over the copolymer molecular parameters have been highlighted as well.

     

Ligand-receptor interactions in chains of colloids: when reactions are limited by rotational diffusion

We discuss the theory of ligand receptor reactions between two freely rotating colloids in close proximity to one other. Such reactions, limited by rotational diffusion, arise in magnetic bead suspensions where the beads are driven into close contact by an applied magnetic field as they align in chainlike structures. By a combination of reaction-diffusion theory, numerical simulations, and heuristic arguments, we compute the time required for a reaction to occur in a number of experimentally relevant situations. We find in all cases that the time required for a reaction to occur is larger than the characteristic rotation time of the diffusion motion tau(rot). When the colloids carry one ligand only and a number n of receptors, we find that the reaction time is, in units of tau(rot), a function simply of n and of the relative surface alpha occupied by one reaction patch alpha = pirC2/(4pir2), where rC is the ligand receptor capture radius and r is the radius of the colloid.     

Highly Enantioselective Rhodium(I)‐Catalyzed Carbonyl Carboacylations Initiated by C?C Bond Activation

The lactone motif is ubiquitous in natural products and pharmaceuticals. The Tishchenko disproportionation of two aldehydes, a carbonyl hydroacylation, is an efficient and atom‐economic access to lactones. However, these reaction types are limited to the transfer of a hydride to the accepting carbonyl group. The transfer of alkyl groups enabling the formation of C C bonds during the ester formation would be of significant interest. Reported herein is such asymmetric carbonyl carboacylation of aldehydes and ketones, thus affording complex bicyclic lactones in excellent enantioselectivities. The rhodium(I)‐catalyzed transformation is induced by an enantiotopic C C bond activation of a cyclobutanone and the formed rhodacyclic intermediate reacts with aldehyde or ketone groups to give highly functionalized lactones.     

Molecular signal suppression by in situ microextraction in nuclear magnetic resonance spectroscopy

The detailed characterization of complex mixtures by NMR is often hampered by the presence of signals from uninformative compounds, the resonances of which overlap with those of the molecules of interest. We provide here a proof of principle for an approach to NMR signal suppression in complex samples using Molecularly Imprinted Polymers (MIPS). Addition of a few milligrams of polymer to a solution traps the target molecule in typical micromolar to millimolar concentration, thus achieving in situ signal suppression, without altering any other spectral features. This method minimized any manipulation or perturbation of the spectrum and was applied to a complex mixture of known compounds and to a plant extract, in both cases spiked with a compound (bisphenol A), which was subsequently removed by selective binding to a complementary MIP. What is described in this report is comparable with microextraction and may in due course be applied to a large number of analytical challenges. Copyright © 2014 John Wiley & Sons, Ltd.     

Low-temperature H2 sensing in self-assembled organotin thin films

Self-assembled nanoporous tin-based hybrid thin films prepared by the sol-gel method from organically-bridged ditin hexaalkynides detect hydrogen gas from 50 to 200 °C at the 200-10,000 ppm level. This finding opens a fully new class of gas-sensing materials as well as a new opportunity to integrate organic functionality in gas sensing metal oxides.     

Cis and trans selective 1,4-addition of a lithium dithioester enolate to 4-O-TBS-2-cyclohexenone

The 1,4-addition of the lithium enolate of methyldithioacetate (LMDTA) to (+/-)-4-O-TBS-2-cyclohexenone (3) can be varied from being highly 3,4-trans selective to being highly 3,4-cis selective simply by varying the reaction temperature. This stereodivergency allows expedient syntheses of the corresponding trans and cis methyl esters 6t and 6c and derived bicyclic ketolactones 7t and 7c.     

HRMAS NMR spectroscopy combined with chemometrics as an alternative analytical tool to control cigarette authenticity

In this paper, we present for the first time the use of high-resolution magic angle spinning nuclear magnetic resonance (HRMAS NMR) spectroscopy combined with chemometrics as an alternative tool for the characterization of tobacco products from different commercial international brands as well as for the identification of counterfeits. Although cigarette filling is a very complex chemical mixture, we were able to discriminate between dark, bright, and additive-free cigarette blends belonging to six different filter-cigarette brands, commercially available, using an approach for which no extraction procedure is required. Second, we focused our study on a specific worldwide-distributed brand for which established counterfeits were available. We discriminated those from their genuine counterparts with 100 % accuracy using unsupervised multivariate statistical analysis. The counterfeits that we analyzed showed a higher amount of nicotine and solanesol and a lower content of sugars, all endogenous tobacco leaf metabolites. This preliminary study demonstrates the great potential of HRMAS NMR spectroscopy to help in controlling cigarette authenticity.