A New Highly Versatile Handle for Chemistry on a Solid Support: The Pipecolic Linker

The design, synthesis, and potential application of the pipecolic linker is presented. This new versatile handle can immobilize primary, secondary, and aromatic amines, as well as alcohols, phenols, and hydrazides, on a solid support. Compared with other linkers, the anchoring step is easy and efficient. The release of final products from the resin proceeds upon acidic treatment with high purities. The pipecolic linker offers the promise of being using in peptide chemistry to produce peptides modified at the N and C terminus, peptidomimetics, as well as small organic molecules.     

Applicability domains for classification problems: Benchmarking of distance to models for Ames mutagenicity set

The estimation of accuracy and applicability of QSAR and QSPR models for biological and physicochemical properties represents a critical problem. The developed parameter of "distance to model" (DM) is defined as a metric of similarity between the training and test set compounds that have been subjected to QSAR/QSPR modeling. In our previous work, we demonstrated the utility and optimal performance of DM metrics that have been based on the standard deviation within an ensemble of QSAR models. The current study applies such analysis to 30 QSAR models for the Ames mutagenicity data set that were previously reported within the 2009 QSAR challenge. We demonstrate that the DMs based on an ensemble (consensus) model provide systematically better performance than other DMs. The presented approach identifies 30-60% of compounds having an accuracy of prediction similar to the interlaboratory accuracy of the Ames test, which is estimated to be 90%. Thus, the in silico predictions can be used to halve the cost of experimental measurements by providing a similar prediction accuracy. The developed model has been made publicly available at http://ochem.eu/models/1 .     

Nuclear and magnetic structures and magnetic properties of the layered cobalt hydroxysulfate Co5(OH)6(SO4)2(H2O)4 and its deuterated analogue, Co5(OD)6(SO4)2(D2O)4

The structures (nuclear and magnetic), magnetic properties (2-300 K, 1-10(4) bar), and heat capacity of the layered ferromagnet Co5(OH)6(SO4)2(H2O)4 are reported. The crystal structure consists of brucite-like M(II)-OH layers of edge-sharing octahedra, but having two different Co sites, which are pillared by ...O3SO-Co(H2O)4-OSO3.... The absorption spectrum confirms the presence of divalent Co, and by comparison of the two isotopic materials, the assignment of the vibrational spectra is proposed. The magnetic properties are those of a ferromagnet with a Curie temperature of 14 K. Temperature and field dependence magnetization data taken on an aligned sample suggest an easy-plane magnet. The Curie temperature increases linearly with pressure at a rate of +0.12 K/kbar, suggesting small progressive and uniform modifications of the Co-Co exchange interactions. Rietveld refinement of the neutron powder diffraction data and consideration of a group analysis reveal the direction of the moments of the Co within the layer to be along the b-axis, with a maximum moment of 3.33 micro(B) per cobalt. Those of the pillars remain random. Estimation of the entropy from the heat capacity data accounts for the presence of four ordered moments of Co with spin 1/2 at the long-range ordering temperature, while the moment of the pillaring Co contributes only at lower temperature due to the increase of the internal field as the temperature is lowered. The purely 2D-magnetic ordering in an easy-plane magnet, evidenced by neutron diffraction and heat capacity, challenges the existing theories and is a rare example of a single-layer magnet.     

Convex analysis and non-trivial invariant subspaces

Positivity - We establish sufficient conditions for the existence of invariant subspaces for operators on real Banach spaces, and we investigate the behaviour of operators without such subspaces....     

Revisiting Energy Release Rates in Brittle Fracture

We revisit in a 2d setting the notion of energy release rate, which plays a pivotal role in brittle fracture. Through a blow-up method, we extend that notion to crack patterns which are merely closed sets connected to the crack tip. As an application, we demonstrate that, modulo a simple meta-stability principle, a moving crack cannot generically kink while growing continuously in time. This last result potentially renders obsolete in our opinion a longstanding debate in fracture mechanics on the correct criterion for kinking.     

An experimental evaluation of two effective medium theories for ultrasonic wave propagation in concrete

This study compares ultrasonic wave propagation modeling and experimental data in concrete. As a consequence of its composition and manufacturing process, this material has a high elastic scattering (sand and aggregates) and air (microcracks and porosities) content. The behavior of the "Waterman-Truell" and "Generalized Self Consistent Method" dynamic homogenization models are analyzed in the context of an application for strong heterogeneous solid materials, in which the scatterers are of various concentrations and types. The experimental validations of results predicted by the models are carried out by making use of the phase velocity and the attenuation of longitudinal waves, as measured by an immersed transmission setup. The test specimen material has a cement-like matrix containing spherical inclusions of air or glass, with radius close to the ultrasonic wavelength. The models are adapted to the case of materials presenting several types of scattering particle, and allow the propagation of longitudinal waves to be described at the scale of materials such as concrete. The validity limits for frequency and for particle volume ratio can be approached through a comparison with experimental data. The potential of these homogenization models for the prediction of phase velocity and attenuation in strongly heterogeneous solids is demonstrated.     

Effects of perfluorocarbon gases on the size and stability characteristics of phospholipid-coated microbubbles: osmotic effect versus interfacial film stabilization

Micrometer-sized bubbles coated with phospholipids are used as contrast agents for ultrasound imaging and have potential for oxygen, drug, and gene delivery and as therapeutic devices. An internal perfluorocarbon (FC) gas is generally used to stabilize them osmotically. We report here on the effects of three relatively heavy FCs, perfluorohexane (F-hexane), perfluorodiglyme (F-diglyme ), and perfluorotriglyme (F-triglyme), on the size and stability characteristics of microbubbles coated with a soft shell of dimyristoylphosphatidylcholine (DMPC) and on the surface tension and compressibility of DMPC monolayers. Monomodal populations of small bubbles (~1.3 ± 0.2 μm in radius, polydispersivity index ~8%) were prepared by sonication, followed by centrifugal fractionation. The mean microbubble size, size distribution, and stability were determined by acoustical attenuation measurements, static light scattering, and optical microscopy. The half-lives of F-hexane- and F-diglyme-stabilized bubbles (149 ± 8 and 134 ± 3 min, respectively) were about 2 times longer than with the heavier F-triglyme (76 ± 7 min) and 4-5 times longer than with air (34 ± 3 min). Remarkably, the bubbles are smaller than the minimal size values calculated assuming that the bubbles are stabilized osmotically by the insoluble FC gases. Particularly striking is that bubbles 2 orders of magnitude smaller than the calculated collapse radius can be prepared with F-triglyme, while its very low vapor pressure prohibits any osmotic effect. The interface between an aqueous DMPC dispersion and air, or air (or N(2)) saturated with the FCs, was investigated by tensiometry and by Langmuir monolayer compressions. Remarkably, after 3 h, the tensions at the interface between an aqueous DMPC dispersion (0.5 mmol L(-1)) and air were lowered from ~50 ± 1 to ~37 ± 1 mN m(-1) when F-hexane and F-diglyme were present and to ~40 ± 1 mN m(-1) for F-triglyme. Also noteworthy, the adsorption kinetics of DMPC at the interface, as obtained by dynamic tensiometry, were accelerated up to 3-fold when the FC gases were present. The compression isotherms show that all these FC gases significantly increase the surface pressure (from ~0 to ~10 mN m(-1)) at large molecular areas (70 ?(2)), implying their incorporation into the DMPC monolayer. All three FC gases increase the monolayer's collapse pressures significantly (~61 ± 2 mN m(-1)) as compared to air (~54 ± 2 mN m(-1)), providing for interfacial tensions as low as ~11 mN m(-1) (vs ~18 mN m(-1) in their absence). The FC gases increase the compressibility of the DMPC monolayer by 20-50%. These results establish that, besides their osmotic effect, FC gases contribute to bubble stabilization by decreasing the DMPC interfacial tension, hence reducing the Laplace pressure. This contribution, although significant, still does not suffice to explain the large discrepancy observed between calculated and experimental bubble half-lives. The case of F-triglyme, which has no osmotic effect, indicates that its effects on the DMPC shell (increased collapse pressure, decreased interfacial tension, and increased compressibility) contribute to bubble stabilization. F-hexane and F-diglyme provided both the smallest mean bubble sizes and the longest bubble half-lives.     

Supercritical adsorption of nitrogen on EcoSorb-activated carbon at temperatures up to 383?K and pressures up to 2?MPa

Single adsorption isotherms and differential enthalpies of adsorption of nitrogen were measured on a microporous-activated carbon at various temperatures. A new way for calculating the differential enthalpies of adsorption is presented, and the results obtained were compared to those obtained by the isosteric method derived from the equilibrium data using the Clausius?CClapeyron equation. The measurements were made thanks to a coupled thermostated calorimetric?Cmanometric apparatus which can be operated for pressures up to 2.5?MPa and temperatures from 303 to 423?K. This article provides experimental data which can be used for the adjustment of interaction potential in computational simulations for supercritical adsorption.     

Measured wavenumber: frequency spectrum associated with acoustic and aerodynamic wall pressure fluctuations

Direct measurements of the wavenumber-frequency spectrum of wall pressure fluctuations beneath a turbulent plane channel flow have been performed in an anechoic wind tunnel. A rotative array has been designed that allows the measurement of a complete map, 63×63 measuring points, of cross-power spectral densities over a large area. An original post-processing has been developed to separate the acoustic and the aerodynamic exciting loadings by transforming space-frequency data into wavenumber-frequency spectra. The acoustic part has also been estimated from a simple Corcos-like model including the contribution of a diffuse sound field. The measured acoustic contribution to the surface pressure fluctuations is 5% of the measured aerodynamic surface pressure fluctuations for a velocity and boundary layer thickness relevant for automotive interior noise applications. This shows that for aerodynamically induced car interior noise, both contributions to the surface pressure fluctuations on car windows have to be taken into account.