An investigation on microscopic and macroscopic stability phenomena of composite solids with periodic microstructure

An analysis of the effects of microscopic instabilities on the homogenized response of heterogeneous solids with periodic microstructure and incrementally linear constitutive law is here carried out. In order to investigate the possibility to obtain a conservative prediction of microscopic primary instability in terms of homogenized properties, novel macroscopic constitutive stability measures are introduced, corresponding to the positive definiteness of the homogenized moduli tensors relative to a class of conjugate stress–strain pairs.Numerical simulations, addressed to hyperelastic microstructural models representing cellular solids and reinforced composites, are worked out through the implementation of an innovative one-way coupled finite element formulation able to determine sequentially the principal equilibrium solution, the incremental equilibrium solutions providing homogenized moduli and the stability eigenvalue problem solution, for a given monotonic macrostrain path. Both uniaxial and equibiaxial loading conditions are considered.The exact microscopic stability region in the macrostrain space, obtained by taking into account microstructural details, is compared with the macroscopic stability regions determined by means of the introduced macroscopic constitutive measures. These results highlight how the conservativeness of the adopted macroscopic constitutive stability measure with respect to microscopic primary instability, strictly depends on the type of loading condition (tensile or compressive) and the kind of microstructure.     

Preparation of monohalopyrroles

Monobromo-, monochloro- and monoiodopyrroles are obtained in excellent yields by using N-halosuccinimides in dimethylformamide as halogenating agents.     

Solution grown isotactic polystyrene crystals. I. Degree and distribution of crystallinity; thermal stability

The subject of this paper is the degree of crystallinity and annealing behavior of solution grown single crystals of isotactic polystyrene (IPS) in relation to the fold length, an enquiry which acquires special significance in view of the fact that previously the fold length had been found to be identical over a wide range of crystallization temperatures (T_c). It was found that both crystallinity and thermal stability increase with T_c even over the range of constant fold length thus invalidating the usual assumption that the fold length and crystal properties are uniquely correlated. Further, the crystallinity figures as measured by conventional calorimetry are very low (<50% throughout) which by conventional ideas would require an unrealistically thick amorphous surface layer. However, the “linear crystallinity” (crystal core thickness as determined from x-ray linewidths) is much larger, commensurate with crystallinities in single crystals from other materials. It is suggested that this is the more relevant figure for the subdivision of the lamellas into crystal core and surface layer. The additional amorphous content being otherwise accommodated. Further, this “linear crystallinity” is broadly unaffected by fold length changes induced by heat annealing. The thermal stability (including annealing ability) of the crystals differs markedly whether T_c is above or below ～60°C, a T_c value which is in the range where the fold length is constant, but corresponds to a maximum in the crystallization rate. Possible connections between crystallization conditions and the stability of the resulting crystals (fold length considerations apart) are pointed out.     

Quantitative evaluation for brain CT/MRI coregistration based on maximization of mutual information in patients with focal epilepsy investigated with subdural electrodes

Patients with drug-resistant focal epilepsy may require intracranial investigations with subdural electrodes. These must be correctly localized with respect to the brain cortical surface and require appropriate monitoring. For this purpose, coregistration techniques, which fuse preimplantation 3D magnetic resonance imaging scans with postimplantation computed tomography scans, have been implemented. In order to reduce localization errors due to the fusion process, we used a coregistration method based on the maximization of mutual information (MI) in 11 patients with extratemporal epilepsy who were invasively investigated. Our registration method is based on three processing steps: rigid-body transformation for coregistration, computation of MI as a similarity measure and the use of the Downhill Simplex optimization method. After consistency analysis, the shift of the registration method reached 0.14+/-0.27 mm in translation and 0.03+/-0.14 degrees in rotation, and the accuracies assessed on voxels of skull surface and voxels of the center of the brain volume were 1.42+/-0.61 and 1.15+/-0.53 mm, respectively. The accuracy of the fusion process reached submillimeter range, and results were considered reliable for surgical planning in all studied patients.     

Plasma proteomics for biomarker discovery: a study in blue

The performance of Cibacron Blue dye (HiTrapBlue or Affigel Blue) in depleting albumin from plasma, as a pre-treatment for biomarker searching in the low-abundance proteome, is here assessed. It is shown that (i) co-depletion of non-albumin species is an ever-present hazard; (ii) the only proper eluant able to release quantitatively the proteins bound to the dye is boiling 4% SDS-25 mM DTT, an ion shock (2 M NaCl) being quite ineffective in releasing the low-abundance species tightly bound to the dye moiety; (iii) the mechanism of dye-protein interaction, after an initial ion-ion docking, is a robust hydrophobic interaction, which progressively augments at lower and lower pH values; (iv) at pH 2.2 in the presence of 0.1% TFA, the blue resin behaves, for all practical purposes, just as a reverse-phase chromatography column, since all residual proteins present in plasma are completely harvested. However Cibacron Blue technology should not necessarily be discarded: As long as also the plasma fraction adsorbed is properly released and analyzed, together with the flow through, one should be able to perform a viable analysis of the low-abundance proteome.     

Nucleophilic substitutions in the isoindole series as a valuable tool to synthesize derivatives with antitumor activity

A novel synthetic approach to the synthesis of 3-substituted isoindoles through nucleophilic substitution of 3-halo derivatives by charged carbon, and neutral nitrogen, oxygen, and sulfur nucleophiles, assisted by a 1-acyl group, is reported. Aryl-thio-isoindoles, obtained through a direct nucleophilic substitution with sulfur nucleophiles, showed cytotoxic activity, with GI₅₀ values from micromolar to sub-micromolar concentrations, against the total number of cell lines investigated.     

Thermal behaviour and electrochemical properties of bis(trifluoromethanesulfonyl)amide and dodecatungstosilicate viologen dimers

We report the synthesis and characterization of dimeric viologen salts (1',1'-(alkane-1,n-diyl)bis(1-ethyl-4,4'-bipyridinium) with n = 4-10) with bis(trifluoromethanesulfonyl)amide (bistriflimide, Tf(2)N(-)) as a counteranion. For n = 4, 5 and 6, and for the nonylviologen cation (1,1'-dinonyl-4,4'-bipyridinium) we also prepared salts with the totally inorganic dodecatungstosilicate anion, SiW(12)O(40)(4-), featuring a poly-charged surface and nanosized dimensions. The materials have been characterized by means of calorimetric techniques, X-ray diffraction and solid state NMR and a comparison is made with analogous monomeric viologen salts exhibiting smectic mesophases. A strong odd-even effect is observed in the melting points and in the thermal behaviour of the bistriflimide dimeric systems, similar to what was reported for dipolar calamitic liquid crystal dimers, although the studied viologen dimers are not mesomorphic. By increasing the size of the counteranion we have observed a destabilization of the crystal phases and of the mesophases in favour of a glassy amorphous state. Implications on the design of novel ionic liquid crystals are discussed. The electrochemical behaviour in solution has been investigated by cyclic voltammetry measurements: interestingly, the odd-even effect is clearly visible also in the redox potentials. The spin-pairing of the viologen radical cations formed at each end of the dimer is responsible for the observed redox trend. Insights on the structure of the spin-paired dimer have been obtained by DFT calculations.     

Analytical performances of a DNA-ligand system using time-resolved fluorescence for the determination of ochratoxin A in wheat

The analytical performances of a novel DNA-ligand system using the time-resolved fluorescence (TRF) response of ochratoxin A (OTA)-terbium-DNA aptamer interaction were tested for the quantitative determination of OTA in wheat. Wheat was extracted with acetonitrile/water (60:40, v/v) followed by clean-up through affinity columns containing a DNA-aptamer-based oligosorbent. Then, OTA was detected by TRF spectroscopy after reaction with a terbium fluorescent solution containing the DNA-aptamer probe. The entire procedure was performed in less than 30 min, including sample preparation, and allowed analysis of several samples simultaneously with a 96-well microplate reader. The average recovery from samples spiked with 2.5-25 μg kg(-1) OTA was 77%, with a relative standard deviation lower than 6% and a quantification limit of 0.5 μg kg(-1). Comparative analyses of 29 naturally contaminated (up to 14 μg kg(-1)) wheat samples using the aptamer-affinity column/TRF method or the immunoaffinity column/high-performance liquid chromatography method showed good correlation (r = 0.985) in the range tested. The trueness of the aptamer-based method was additionally assessed by analysis of two quality control wheat materials for OTA. The DNA-ligand system is innovative, simple and rapid, and can be used to screen large quantities of samples for OTA contamination at levels below the EU regulatory limit with analytical performances satisfying EU criteria for method acceptability.