A preliminary study exploring the mechanical properties of normal and Mgp-deficient mouse femurs during early growth.

Matrix Gla protein (MGP) is mostly known to be a calcification inhibitor, as its absence leads to ectopic calcification of different tissues such as cartilage or arteries. MGP deficiency also leads to low bone mass and delayed bone growth. In the present contribution, we investigate the effect of MGP deficiency on the structural and material mechanical bone properties by focusing on the elastic response of femurs undergoing three-points bending. To this aim, biomechanical tests are performed on femurs issued from Mgp-deficient mice at 14, 21, 28, and 35 days of postnatal life and compared to healthy control femurs. µCT acquisitions enable to reconstruct bone geometries and are used to construct subject-specific finite element models avoiding some of the reported limitations concerning the use of beam-like assumptions for small bone samples. Our results indicate that MGP deficiency may be associated to differences in both structural and material properties of femurs during early stages of development. MGP deficiency appears to be related to a decrease in bone dimensions, compensated by higher material properties resulting in similar structural bone properties at P35. The search for a unique density-elasticity relationship based on calibrated bone mineral density (BMD) indicates that MGP deficiency may affect bone tissue in several ways, that may not be represented uniquely from the quantification of BMD. Despite of its limitation to elastic response, the present preliminary study reports for the very first time the mechanical skeletal properties of Mgp-deficient mice at early stages of development.

The Impact of Chemical-Mechanical Ex Situ Aging on PFSA Membranes for Fuel Cells.

A proton-exchange membrane fuel cell (PEMFC) constitutes today one of the preferred technologies to promote hydrogen-based alternative energies. However, the large-scale deployment of PEMFCs is still hampered by insufficient durability and reliability. In particular, the degradation of the polyelectrolyte membrane, caused by harsh mechanical and chemical stresses experienced during fuel cell operation, has been identified as one of the main factors restricting the PEMFC lifetime. An innovative chemical-mechanical ex situ aging device was developed to simultaneously expose the membrane to mechanical fatigue and an oxidizing environment (i.e., free radicals) in order to reproduce conditions close to those encountered in fuel cell systems. A cyclic compressive stress of 5 or 10 MPa was applied during several hours while a degrading solution (H2O2 or a Fenton solution) was circulated in contact with the membrane. The results demonstrated that both composite Nafion™ XL and non-reinforced Nafion™ NR211 membranes are significantly degraded by the conjoint mechanical and chemical stress exposure. The fluoride emission rate (FER) was generally slightly lower with XL than with NR211, which could be attributed to the degradation mitigation strategies developed for composite XL, except when the pressure level or the aging duration were increased, suggesting a limitation of the improved durability of XL.

Generalized gaussian model for uniaxial rotational motion: application to the calculation of spectroscopic responses.

An exact model aimed at describing uniaxial rotational motions, based on a rotational adapted Gaussian statistics, is presented. In its simplest form, it depends on only two parameters, an order parameter which can vary from 1 (perfect order) to 0 (isotropic diffusion) and a time-dependent correlation parameter rho which varies from 1 to 0 between initial and infinite times. This model yields closed form expressions for the correlation functions relevant to the main spectroscopic techniques (dielectric absorption, light and neutron scattering, NMR line shape, spin-lattice relaxation, etc.) for all values of the two parameters. According to the functional form postulated for rho(t), in particular forms decaying as power laws at long times, one obtains shapes for the spectroscopic correlation functions and spectra that are similar to those experimentally observed in a large variety of complex systems (liquid crystals, polymers, gels, and amorphous and glassy materials), especially in confined geometries, which often resemble "stretched" exponentials. A simple way to introduce time coherent effects through a modification of rho(t) is proposed. Examples of theoretical correlation functions and spectra are presented. Important remarks concerning the application of this model to the analysis of real data are made. This model is the rotational analogue of the Gaussian translational model developed recently (Volino et al. J. Phys. Chem B 2006, 110, 11217).

Water dynamics in ionomer membranes by field-cycling NMR relaxometry.

The dynamic behavior of water within two types of ionomer membranes, Nafion and sulfonated polyimides, has been investigated by field-cycling nuclear magnetic relaxation. This technique, applied to materials prepared at different hydration levels, allows to probe the proton motion on a time scale of the microsecond. The NMR longitudinal relaxation rate R(1) measured over three decades of Larmor angular frequencies omega is particularly sensitive to the host-water interactions and thus well suited to study fluid dynamics in restricted geometries. In the polyimide membranes, we have observed a strong dispersion of R(1)(omega) following closely a 1/sqrt[omega] law in a low-frequency range (correlation times from 0.1 to 10 micros). This is indicative of a strong interaction of water with "interfacial" hydrophilic groups of the polymeric matrix (wetting situation). On the contrary, in the Nafion, we observed weak variations of R(1)(omega) at low frequency. This is typical of a nonwetting behavior. At early hydration stages, the proton-proton inter-dipolar contribution to R(1)(omega) evolves logarithmically, suggesting a confined bidimensional diffusion of protons in the microsecond time range. Such an evolution is lost at higher swelling where a plateau related to 3D diffusion is observed.

Gaussian model for localized translational motion: application to incoherent neutron scattering.

A simple model based on Gaussian statistics, aimed at describing localized diffusive translational motion in one, two, and three dimensions is presented and used to calculate the corresponding incoherent neutron scattering laws. In the time domain, these laws are closed form mathematical functions. In the frequency domain, some of these laws can be expressed as an infinite series depending on one single index. Owing to this relative simplicity, such a model can advantageously replace previous models such as diffusion on a segment, inside a circle and inside a sphere with an impermeable surface, to analyze neutron quasielastic scattering data associated with molecular motions in confined media. It may also be more realistic when the confinement is defined by soft, ill-defined boundaries.

Water dynamics in ionomer membranes by field-cycling NMR relaxometry.

The dynamic behavior of water within two types of ionomer membranes, Nafion and sulfonated polyimide, has been investigated by field-cycling nuclear magnetic relaxation. This technique, applied to materials prepared at different hydration levels, allows the proton motion on a time scale of microseconds to be probed. The NMR longitudinal relaxation rate R(1) measured over three decades of Larmor angular frequencies omega is particularly sensitive to the host-water interactions and thus well-suited to study fluid dynamics in restricted geometries. In the polyimide membranes, we have observed a strong dispersion of R(1)(omega) following closely a 1/square root omega law in a low-frequency range (correlation times from 0.1 to 10 micros). This is indicative of a strong interaction of water with "interfacial" hydrophilic groups of the polymeric matrix (wetting situation). Variations of the relaxation rates with water uptake reveal a two-step hydration process: solvation and formation of disconnected aqueous clusters near polar groups, followed by the formation of a continuous hydrogen bond network. On the contrary, in the Nafion we observed weak variations of R(1)(omega) at low frequencies. This is typical of a nonwetting behavior. At early hydration stages, R(1)(omega) evolves logarithmically, suggesting a confined bidimensional diffusion of protons in the microsecond time range. Such an evolution is lost at higher swelling where a plateau related to three-dimensional diffusion is observed.