Crack Initiation in Brittle Materials

In this paper we study the crack initiation in a hyper-elastic body governed by a Griffith-type energy. We prove that, during a load process through a time-dependent boundary datum of the type t → t g(x) and in the absence of strong singularities (e.g., this is the case of homogeneous isotropic materials) the crack initiation is brutal, that is, a big crack appears after a positive time t _i > 0. Conversely, in the presence of a point x of strong singularity, a crack will depart from x at the initial time of loading and with zero velocity. We prove these facts for admissible cracks belonging to the large class of closed one-dimensional sets with a finite number of connected components. The main tool we employ to address the problem is a local minimality result for the functional where , k > 0 and f is a suitable Carathéodory function. We prove that if the uncracked configuration u of Ω relative to a boundary displacement ψ has at most uniformly weak singularities, then configurations (uΓ, Γ) with small enough are such that .     

Nucleation of Polypropylene Crystallization with Gold Nanoparticles. Part 2: Relation between Particle Morphology and Nucleation Activity

The influence of gold nanoparticle morphology on nucleation of isotactic polypropylene (PP) crystallization was investigated. Previous experiments indicated certain nucleation activity of gold nanoparticles, varying with their size. In this work, eight types of gold micro/nanoparticles were used: vacuum-sputtered nanostructures (nanoparticles, nanoislands, and nanolayers), chemically prepared isometric gold nanocrystals (5, 20, and 100 nm diameters), and two types of gold microcrystals with well-developed crystal facets [with (100) and (111) facets, respectively]. To minimize the effect of particle agglomeration, we used our recently introduced sandwich method, in which the nucleating agent was deposited between thin PP films and the nucleation was evaluated by polarized light microscopy (PLM), X-ray scattering (WAXS), and differential scanning calorimetry (DSC). The nucleation activity of Au particles in PP was lower than it might be expected from the previous studies and depended on their morphology. The nucleation activity of Au microcrystals with well-developed facets was higher than the activity of non-faceted Au nanocrystals.     

Measurement of the relative air permeability of compacted earth in the hygroscopic regime of saturation

The hygroscopic behavior of earthen materials has been extensively studied in the past decades. However, while the air flow within their porous network may significantly affect the kinetics of vapor transfer and thus their hygroscopic performances, few studies have focused on its assessment. For that purpose, a key parameter would be the gas permeability of the material, and its evolution with the relative humidity of the air. Indeed, due to the sorption properties of earthen material, an evolution of the water content, and thus of relative permeability, are foreseeable if the humidity of in-pore air changes. To fill this gap, this paper presents the measurement of relative permeabilities of a compacted earth sample with a new experimental set-up. The air flow through the sample is induced with an air generator at controlled flow rate, temperature, and humidity. The sample geometry was chosen in order to reduce, as much as possible, its heterogeneity in water content, and the tests were realized for several flow rates. The results, which show the evolution of gas permeability with the relative humidity of the injected air and with the water content of the material, either in adsorption or in desorption, were eventually successfully compared to predictions of the well-known Corey's law.     

Experimental validation of single-iteration multigrid wavefront reconstruction at the Palomar Observatory

Single-iteration multigrid (SIMG) wavefront reconstruction schemes were implemented and validated on the adaptive optics system at the Hale 5.1 m telescope at the Palomar Observatory. Results indicate that even the simplest such method produces a performance indistinguishable from that of the standard least-squares reconstructor for both bright and dim guide stars. SIMG provides a dramatic reduction in computational cost when compared to vector-matrix multiplication and can be implemented in parallel, making it the obvious choice for reconstruction in future large-scale adaptive optics systems.     

Conditions for identical position of optimal image plane for axial imaging with different values of f-number

By analysis of the dependence of longitudinal spherical aberration on the numerical aperture, it is possible to find such values of the numerical aperture, where spherical aberration is zero. Such values of the numerical aperture are called correction zones. The work theoretically analyses the described problem and equations are given for wave aberration coefficients using correction zones for spherical aberration of the third and the fifth order. Our work presents an analysis of optimal values of correction zones and an optimal position of the center of the reference sphere based on the variance of wave aberration for the image quality evaluation. Relations are described for calculation of correction zones of an optical system having an identical position of the optimal image plane for two values of the f-number. The analysis of optical systems using correction zones is performed on an example.     

Continuous electrochemical monitoring of nitric oxide production in murine macrophage cell line RAW 264.7

In this study, we realized the continual and long-term electrochemical detection of NO production by stimulated macrophages using modified porphyrinic microsensor. The NO release from RAW 264.7 cells stimulated by lipopolysaccharide started 5 h after the lipopolysaccharide administration. After reaching its maximum at the sixth hour, the stable level of NO production was observed between the seventh and 12th hour of the experiment. This phase was followed by a gradual decline in NO production. A close correlation between the NO signal detected with microelectrode and nitrite accumulation, which had been determined in supernatants removed from stimulated cells, was observed. This finding was utilized for the calibration of the electrochemical experiment. The presence of iNOS enzyme, which constitutes a main requirement for NO production by stimulated macrophages, was confirmed by Western blot analysis of iNOS protein expression at key time points of the corresponding electrochemical experiment. The capability of our microsensor to instantaneously monitor the changes in the NO production by stimulated RAW 264.7 cells was demonstrated by the immediate decrease in the signal due to NO as a response to the addition of iNOS inhibitor into the cell culture medium. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Gas hydrates in low water content gases: Experimental measurements and modelling using the CPA equation of state

In this communication, new experimental data are reported for the water content of methane and two synthetic gas mixtures in equilibrium with hydrates at pressures range from 5 to 40 MPa and temperature down to 251.65 K. The measurements have been made on equilibrated samples taken from a high-pressure variable volume hydrate cell using a new analyser based upon tuneable diode laser absorption spectroscopy (TDLAS) technology. A statistical thermodynamic approach, with the Cubic-Plus-Association equation of state, is employed to model the phase equilibria. The hydrate-forming conditions are modelled by the solid solution theory of van der Waals and Platteeuw. The thermodynamic model was used to predict the water content of methane and synthetic gases in equilibrium with gas hydrates.     

Novel Domino Reactions of (Z,Z)-2,2′-Thiobis(1,3-diarylprop-2-en-1-ones) with Acetylacetone and Ethyl Acetoacetate: Stereoselective Synthesis of Highly Functionalized Dihydrofurans

The domino reactions of (Z,Z)-2,2′-thiobis(1,3-diarylprop-2-en-1-ones) with acetylacetone and ethyl acetoacetate in the presence of sodium ethoxide afforded the corresponding 4,5-dihydrofurans stereoselectively in moderate yields presumably via a Michael addition–enolization–displacement sequence.     

Parameters for Irreversible Inactivation of Monoamine Oxidase

The irreversible inhibitors of monoamine oxidases (MAO) slow neurotransmitter metabolism in depression and neurodegenerative diseases. After oxidation by MAO, hydrazines, cyclopropylamines and propargylamines form a covalent adduct with the flavin cofactor. To assist the design of new compounds to combat neurodegeneration, we have updated the kinetic parameters defining the interaction of these established drugs with human MAO-A and MAO-B and analyzed the required features. The K_i values for binding to MAO-A and molecular models show that selectivity is determined by the initial reversible binding. Common to all the irreversible inhibitor classes, the non-covalent 3D-chemical interactions depend on a H-bond donor and hydrophobic-aromatic features within 5.7 angstroms apart and an ionizable amine. Increasing hydrophobic interactions with the aromatic cage through aryl halogenation is important for stabilizing ligands in the binding site for transformation. Good and poor inactivators were investigated using visible spectroscopy and molecular dynamics. The initial binding, close and correctly oriented to the FAD, is important for the oxidation, specifically at the carbon adjacent to the propargyl group. The molecular dynamics study also provides evidence that retention of the allenyl imine product oriented towards FADH⁻ influences the formation of the covalent adduct essential for effective inactivation of MAO.