Arylene bisimides with triarylamine N-substituents as new solution processable organic semiconductors: Synthesis,spectroscopic, electrochemical and electronic properties

New solution processable organic semiconductors, consisting of pyrromelitic, naphthalene or perylene bisimide core and triarylamine N-substituents, have been synthesized. All three compounds are electrochemically active and undergo quasi-reversible oxidation and reduction as evidenced by cyclic voltammetry investigations. The oxidation process involves the transformation of the triarylamine substituents into radical cations as proven spectroscopically and spectroelectrochemically. The reduction process occurs at the arylene bisimide core leading to the formation of a radical anion and eventually a dianion in the second step. These findings are in perfect agreement with the DFT calculations which show that in the synthesized molecules the HOMO orbital is located on the triarylamine moiety whereas the LUMO one on the bisimide core. In all molecules studied the electrochemically determined ionization potential (IP) is slightly higher than 5.0 eV whereas in naphthalene and perylene derivatives the electron affinity (EA) is close to ?3.9 eV. These values fulfill the requirements for n-type (electron) semiconductors in air operating n-channel field effect transistors (FETs) as well as for p-type (hole) conductors in p-channel FETs. To verify whether the newly synthesized compounds exhibit the expected electrical transport properties all organic (CYTOP dielectric) test transistors were fabricated. All three semiconductors showed no field effect in the n-channel configuration. To the contrary, they could be used in p-channel FETs showing, in the saturation regime, the hole mobility approaching 10^?4 cm² V^?1 s^?1 – the value which slightly exceeds that measured for low molecular weight, amorphous triarylamine semiconductors.     

First-principles study of nickel-silicides ordered phases

We present a study of nickel-silicides ordered alloys by means of first-principles calculations. Emphasis was put on the phases (low and high temperatures) identified in the binary phase diagram, namely: Ni₃Si-β₁, -β₂, and -β₃, Ni₃₁Si₁₂-γ, Ni₂Si-δ, -θ, Ni₃Si₂-?, NiSi-MnP and NiSi₂-α. In addition, some common structures are computed for information: L1₂, D0₃ and D0₂₂. The simulations reproduce with a high accuracy lattice parameters and formation energies of main experimental structures, except for β₂ and β₃. Our results clarify the crystallographic nature of the γ structure, and the comparison of experimental Raman spectra and vibrational calculations will help experimentalists to identify without ambiguity NiSi₃ structures.     

A double linear driving force approximation for non-isothermal mass transfer modeling through bi-disperse adsorbents

The aim of this paper is to derive a double LDF non-isothermal model to describe mass transfer through a fixed bed of bi-disperse adsorbent pellets. Firstly, we perform an analysis concerning the different way the composition within the pellets can be described and the consequence on the model structure and compactness. Secondly, we present a bed model including a simplified intra-particle model that is based on a double LDF approximation. This bi-disperse pellet model reduces the number of variables and parameters that are needed. This simplified model is used to simulate breakthroughs of a methane/carbon dioxide mixture over a 5 A zeolite and of a 2,2-dimethylbutane/2-methylpentane mixture over a silicalite molecular sieve. It is also compared with a more detailed model based on Stefan-Maxwell theory that we have previously developed.     

Four-week short chain fructo-oligosaccharides ingestion leads to increasing fecal bifidobacteria and cholesterol excretion in healthy elderly volunteers

Background  

Short-chain fructo-oligosaccharides (scFOS) are increasingly used in human diet for their prebiotic properties. We aimed at investigating the effects of scFOS ingestion on the colonic microflora and oro-fecal transit time in elderly healthy humans.     

How an Ant Manages to Display Individual and Colonial Signals by Using the Same Channel

Cuticular hydrocarbons are used by some ants to discriminate nestmates from nonnestmates. Every member of the colony bears the same pattern because they are continuously exchanged among nestmates. The postpharyngeal gland (PPG) stores the blend of hydrocarbons and is involved in the distribution of this common mixture. However, some individuals might display individual information on the cuticle (such as a chemical signal of fertility) that must not be mixed within the common pool. We investigated how this paradox is solved in the ant Pachycondyla goeldii by analyzing the nature and localization of colonial and fertility signals. Workers in a queenless condition showed a dominance hierarchy that was correlated with ovarian development. Hydrocarbons from the cuticle and the PPG analyzed by gas chromatography (GC) and identified by GC-mass spectrometry showed a clear discrimination among colonies, supporting the involvement of the PPG in the colonial identity signal. We identified and selected 11 cuticular hydrocarbons that permitted us to discriminate ovarian development classes and that might function as a fertility signal. They allowed clear colony discrimination as well, which suggests that the two signals (the individual signal of fertility and the common signal of colony identity) can be conveyed by the same compounds. However, the hydrocarbons in the PPG did not discriminate among ovarian developmental classes, suggesting that the portion of variation in the cuticular hydrocarbons constituting the fertility signal is superimposed on the signal of colony identity.     

The role of dermabrasion and chemical peels in the treatment of patients with xeroderma pigmentosum

We describe our experience with two patients with xeroderma pigmentosum who underwent periodic trichloroacetic acid chemical peels. One also received a full-face dermabrasion. The effect of chemical peeling was more transient than dermabrasion but was associated with less morbidity. Both chemical peeling and dermabrasion provided a prophylactic effect against the development of skin malignancies; the latter had a more pronounced effect.     

Hydrothermal Synthesis and Characterization of Europium-doped Barium Titanate Nanocrystallites

Nano-Micro Letters - Barium titanate nanocrystallites were synthesized by a hydrothermal technique from barium chloride and tetrabutyl titanate. Single-crystalline cubic perovskite BaTiO3...     

Electrochemical detection of oligopeptides at silicon-fabricated micro-liquid/liquid interfaces

The detection of peptides is an important bioanalytical challenge, as they are a generic class of potent molecules of biomedical and biopharmaceutical significance. In this work, the electrochemistry of seven oligopeptides at microscaled interfaces between two immiscible electrolyte solutions (microITIES) was investigated. Their transfer across the polarized interface was assisted by dibenzo-18-crown-6 (DB18C6). The ion transfer potentials of these oligopeptides were dependent on their hydrophobicities and their interaction with DB18C6. Micropore arrays, which were fabricated in silicon by a combination of wet and dry etch techniques, were used to enhance mass transfer and thus analytical sensitivities. The use of a gellified organic phase allowed the implementation of voltammetric stripping techniques at the liquid-organogel interface. The combination of interface miniaturization and stripping voltammetry provided limits of detection at submicromolar concentration levels. The sensitivities (calibration graph slopes) were -3205 nA microM(-1) cm(-2) for Phe-Phe, -1791 nA microM(-1) cm(-2) for Leu-Leu, -6014 nA microM(-1) cm(-2) for Lys-Lys, and -9611 nA microM(-1) cm(-2) for Lys-Lys-Lys. Mixtures of peptides were also investigated with this technique, illustrating the possibility to detect certain mixture combinations.     

Determination of Darcian permeability of porous material by infrared spectrometry

The active cooling of aerospace structures can be performed by the use of porous materials. It requires characterizing its permeability to predict the cooling efficiency by means of Computational Fluid Dynamics codes. The Darcian term is generally deduced experimentally from a relationship between the mass flow rate and the pressure drop through the porous media. Due to thermo-chemical process involved in the cooling, the permeability can change. It is currently not possible with common techniques to determine these variations during the flight. This paper presents a novel approach taking advantage of well known flow behaviour in chemical reactor engineering in order to propose a real-time in situ quantification of the Darcian permeability. The residence time distribution is analyzed thanks to tracer injection and to associated experimental measures of Infra-Red signals. The IR peak characteristics (height, width, surface, rising and falling gradients) and time delays are analyzed and correlated to physical parameters (mass flow rate, injected mass of tracer, properties of fluids). The peak height and surface and the rising gradient vary linearly in the same sense as the injected tracer mass while the falling gradient varies in the opposite sense. Both gradients decrease with a mass flow rate increase. The time delay between injection and detection of the tracer is quite constant except when changing the fluid nature. A design of experiments allowed estimating quantitatively the influence of each physical parameter on the optical one of the IR signal. Thanks to this first understanding, the Darcian permeability is linked to the observed IR signal. A linear regression is proposed with the peak width which is judged to be the most relevant parameter. Finally, an analytical approach is developed to fit ordinary differential equations to IR peak measures and to correlate the parameters of the law to the Darcian permeability. Several laws (linear, logarithmic and power) are proposed depending on the parameter but the linear regression involving the coefficient noted ?? ₁ is the most promising. One of the advantages of this method is to be able measuring the permeability during the flight and not only on-ground with specific test facility.