Mathematical models for the non‐isothermal Johnson–Segalman viscoelasticity in porous media: stability and wave propagation

We present a nonlinear model for Johnson–Segalman type polymeric fluids in porous media, accounting for thermal effects of Oldroyd‐B type. We provide a thermodynamic development of the Darcy's theory, which is consistent with the interlacement between thermal and viscoelastic relaxation effects and diffusion phenomena. The appropriate invariant convected time derivative for the flux vector and the stress tensor is discussed. This is performed by investigating the local balance laws and entropy inequality in the spatial configuration, within the single‐fluid approach. For constant parameters, our thermomechanical setting is of Jeffreys type with two delay time parameters, and hence, in the linear/linearized version, it is strictly related to phase‐lag theories within first‐order Taylor approximations. A detailed spectral analysis is carried out for the linearized version of the model, with a scrutiny to some significant limit situations, enhancing the stabilizing effects of the dissipative and elastic mechanisms, also for retardation responses. For polymeric liquids, rheological aspects, wave propagation properties and analogies with other theories with lagging are pointed out. Copyright © 2014 John Wiley & Sons, Ltd.     

Determination of Binding Strengths of Host-Guest Complexes in Deep Eutectic Solvents Using Spin Probe Methodology

Electron paramagnetic resonance (EPR) and spin probe methodologies have been employed to study the complexation properties of cyclodextrins (CDs) and cucurbit[n]urils (CB[n]s) in the deep eutectic solvent (DES) choline chloride-urea. In the presence of γ-CD an affinity constant very similar to that measured in water was measured in DES with benzyl-tert-butyl nitroxide (BTBN). With β-CD, complexation of BTBN is significantly depressed, although still maintained. Complexation of TEMPO radical probe by CB[7] or CB[8] was instead almost entirely cancelled in DES. In addition, this methodology enabled for the first time to measure the single rate constants for the association and dissociation processes with CDs in DES.     

Formation of Patches on 3D SAMs Driven by Thiols with Immiscible Chains Observed by ESR Spectroscopy

Beyond stripes : The extreme lipophobicity of perfluorinated chains attached to amphiphilic thiolates triggers the formation of “stars” (or patches) surrounded by amphiphilic alkylthiolates in three‐dimensional self‐assembled monolayers. This strategy led to the first example of a water‐soluble multicompartment monolayer wrapped around a gold core.

     

Synthesis and characterization of a persistent paramagnetic rotaxane based on alpha-cyclodextrin

The synthesis and spectroscopic properties of a novel paramagnetic [2]rotaxane is described. This rotaxane is made from molecules having an alkyl chain flanked by 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) groups. Complexation of sebacoyl chloride by alpha-cyclodextrin followed by reaction with a bulky aminonitroxide resulted in the trapping of the cyclodextrin, threaded by the alkyl chain, thus generating the rotaxane structure. The structure of the paramagnetic [2]rotaxane was fully characterized by ESI-MS, 1D and 2D NMR and ESR spectroscopy.     

Regular submanifolds, graphs and area formula in Heisenberg groups

We describe intrinsically regular submanifolds in Heisenberg groups Hn. Low dimensional and low codimensional submanifolds turn out to be of a very different nature. The first ones are Legendrian surfaces, while low codimensional ones are more general objects, possibly non-Euclidean rectifiable. Nevertheless we prove that they are graphs in a natural group way, as well as that an area formula holds for the intrinsic Hausdorff measure. Finally, they can be seen as Federer-Fleming currents given a natural complex of differential forms on Hn.     

A comparison of carboxypyridine isomers as sensitizers for dye-sensitized solar cells: assessment of device efficiency and stability

Three novel organic dyes (DF13A–C) carrying regioisomeric carboxypyridine anchoring groups were synthesized by means of a multistep synthetic sequence involving a Pd-catalyzed Stille coupling as the key step. The new compounds underwent full spectroscopic, electrochemical, and computational characterization, and their properties were compared with those of a reference compound endowed with a classic cyanoacrylic acid acceptor (DF15). Photovoltaic measurements showed that dye-sensitized solar cells built with dyes DF13A–C as photosensitizers yielded power conversion efficiencies corresponding to 54–63% of those obtained with the reference compound. Determination of desorption pseudo-first order rate constants indicated that isomers DF13B–C, having the nitrogen atom in neighboring position relative to the carboxylic moiety, were removed from TiO₂ more slowly than isomer DF13A or cyanoacrylic derivative DF15, suggesting a possible cooperative effect of the two functional groups on semiconductor binding: such hypothesis was supported by device stability tests carried out on transparent, larger area cells.     

A photoluminescence study of the effects of hydrogen on deep levels in MBE grown GaAlAs:Si

We present a study on low-temperature photoluminescence (PL) of Si-doped

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grown by MBE in the presence and in the absence of a hydrogen backpressure, and post-growth hydrogenated or not, by exposure to a hydrogen plasma. The PL spectra of GaAlAs grown without hydrogen are dominated by transitions involving relatively deep donors and/or acceptors independently on whether the material is post-growth hydrogenated. On the contrary, the spectra of GaAlAs grown in the presence of hydrogen are characterized by recombinations related to excitons and/or to shallow donors and acceptors. Both the in-situ and the ex-situ processes result in PL efficiency enhancements, which are definitely larger (by a factor of up to 20) when the former treatment is used. All of the above results suggest that the ex-situ and the in-situ treatments may affect deep levels of different origin, such as DX centers (related to the band structure of the semiconductor) and levels associated to Al-O complexes, respectively.     

Competition in the carrier capture between InGaAs/AlGaAs quantum dots and deep point defects

The presence of an extrinsic photoluminescence (PL) band peaked at 1.356 eV at low temperature is observed, on a large number of self-assembled InAs and In_0.5Ga_0.5As quantum dot (QD) structures, when exciting just below the GaAs absorption edge. A detailed optical characterization allows us to attribute the 1.356 eV PL band to the radiative transition between the conduction band and the doubly ionized Cu _Ga acceptor in GaAs. A striking common feature is observed in all investigated samples, namely a resonant quenching of the QD-PL when exciting on the excited level of this deep defect. Moreover, the photoluminescence excitation (PLE) spectrum of the 1.356 eV emission turns out to be almost specular to the QD PLE. This correlation between the PL efficiency of the QDs and the Cu centers evidences a competition in the carrier capture arising from a resonant coupling between the excited level of the defect and the electronic states of the wetting layer on which the QDs nucleate. The estimated Cu concentration is compatible with a contamination during the epitaxial growth. Received 13 November 2001 / Received in final form 28 May 2002 Published online 19 July 2002