Stéphan Rouzière

Diffraction techniques and Vibrational spectroscopy opportunities to characterise bones

From a histological point of view, bones that allow body mobility and protection of internal organs consist not only of different organic and inorganic tissues but include vascular and nervous elements as well. Moreover, due to its ability to host different ions and cations, its mineral part represents an important reservoir, playing a key role in the metabolic activity of the organism. From a structural point of view, bones can be considered as a composite material displaying a hierarchical structure at different scales. At the nanometre scale, an organic part, i.e. collagen fibrils and an inorganic part, i.e. calcium phosphate nanocrystals are intimately mixed to assure particular mechanical properties.

High Zn content of Randall's plaque: A μ-X-ray fluorescence investigation

Kidney stone disease, or nephrolithiasis, is a common ailment. Among the different risk factors usually associated with nephrolithiasis are dehydration, metabolic defects (especially with regard to calcium and oxalate). The presence of a mineral deposit at the surface of the renal papilla (termed Randalls plaque) has all been recently underlined. Of note, Randalls plaque is made of the calcium phosphate, carbapatite, and serves as a nucleus for kidney stone formation. The process by which apatite nanocrystals nucleate and form Randalls plaque remains unclear. This paper deals with the possible relationship between trace elements and the formation of this mineral. The investigation has been performed on a set of Randalls plaques, extracted from human kidney stones, through μ-X-ray diffraction and μ-X-ray fluorescence analyses in order to determine the chemical composition of the plaque as well as the nature and the amount of trace elements. Our data provide evidence that Zn levels are dramatically increased in carbapatite of RP by comparison to carbapatite in kidney stones, suggesting that calcified deposits within the medullar interstitium are a pathological process involving a tissue reaction. Further studies, perhaps including the investigation of biomarkers for inflammation, are necessary for clarifying the role of Zn in Randalls plaque formation.

The status of strontium in biological apatites: an XANES/EXAFS investigation

Osteoporosis represents a major public health problem through its association with fragility fractures. The public health burden of osteoporotic fractures will rise in future generations, due in part to an increase in life expectancy. Strontium-based drugs have been shown to increase bone mass in postmenopausal osteoporosis patients and to reduce fracture risk but the molecular mechanisms of the action of these Sr-based drugs are not totally elucidated. The local environment of Sr(2+) cations in biological apatites present in pathological and physiological calcifications in patients without such Sr-based drugs has been assessed. In this investigation, X-ray absorption spectra have been collected for 17 pathological and physiological calcifications. These experimental data have been combined with a set of numerical simulations using the ab initio FEFF9 X-ray spectroscopy program which takes into account possible distortion and Ca/Sr substitution in the environment of the Sr(2+) cations. For selected samples, Fourier transforms of the EXAFS modulations have been performed. The complete set of experimental data collected on 17 samples indicates that there is no relationship between the nature of the calcification (physiological and pathological) and the adsorption mode of Sr(2+) cations (simple adsorption or insertion). Such structural considerations have medical implications. Pathological and physiological calcifications correspond to two very different preparation procedures but are associated with the same localization of Sr(2+) versus apatite crystals. Based on this study, it seems that for supplementation of Sr at low concentration, Sr(2+) cations will be localized into the apatite network.

X-ray scattering determination of the structure of water during carbon nanotube filling.

We present in situ monitoring of water filling of single-walled carbon nanotubes at room temperature, using X-ray scattering. A systematic method is developed to determine the water radial density profile. Water filling is homogeneous below about 5% in mass, whereas it structures into three layers above. These results should motivate further theoretical and simulations studies and allow getting a better understanding of the very peculiar properties of water confined in hydrophobic environment.

Probing magnetic interactions in columnar phases of a paramagnetic gold dithiolene complex

A novel radical gold dithiolene complex exhibits a hexagonal columnar mesophase, as confirmed by optical microscopy, DSC analysis and X-ray diffraction. The extent of delocalization of the spin density in such a complex was analyzed by EPR. Temperature dependent magnetization measurements reveal that the global magnetic moment is remarkably affected at the liquid-crystalline phase transition with a marked hysteresis signature, rare behavior among the few described paramagnetic discotic phases. In addition, these molecules were found to strongly aggregate in solution into one-dimensional fibers with a mean diameter of 60 nm extending over micrometres, leading to the formation of gel-like structures. These fibers are stable and can be isolated on surfaces. The gelation of the system can also be detected by temperature-dependent magnetic measurements.

Tailoring highly oriented and micropatterned clay/polymer nanocomposites by applying an a.c. electric field.

Clay/polymer nanocomposites have recently raised much interest because of their widespread industrial applications. Nevertheless, controlling both clay platelet exfoliation and orientation during polymerization still remains challenging. Herein, we report the elaboration of clay/polymer nanocomposite hydrogels from aqueous suspensions of natural swelling clays submitted to high-frequency a.c. electric fields. X-ray scattering experiments have confirmed the complete exfoliation of the clay sheets in the polymer matrix, even after polymerization. Moreover, polarized light microscopy shows that the clay platelets were perfectly oriented by the electric field and that this field-induced alignment was frozen in by in situ photopolymerization. This procedure allowed us to not only produce uniformly aligned samples but also pattern platelet orientation, at length scales down to 20 μm. This straightforward and cheap nanocomposite patterning technique can be easily extended to a wide range of natural or synthetic inorganic anisotropic particles.

Synchrotron X-ray diffraction experiments with a prototype hybrid pixel detector

A prototype X-ray pixel area detector (XPAD3.1) has been used for X-ray diffraction experiments with synchrotron radiation. The characteristics of this detector are very attractive in terms of fast readout time, high dynamic range and high signal-to-noise ratio. The prototype XPAD3.1 enabled various diffraction experiments to be performed at different energies, sample-to-detector distances and detector angles with respect to the direct beam, yet it was necessary to perform corrections on the diffraction images according to the type of experiment. This paper is focused on calibration and correction procedures to obtain high-quality scientific results specifically developed in the context of three different experiments, namely mechanical characterization of nanostructured multilayers, elastic-plastic deformation of duplex steel and growth of carbon nanotubes.

Diversité chimique des calculs prostatiques : une investigation par MEB et spectroscopie infrarouge

OBJECTIVE Revisiting the chemical diversity of the crystalline phases of prostatic calculi by means of SEM and FT-IR analysis. METHODS A set of 32 prostatic calculi has been studied by FT-IR and SEM. RESULTS FT-IR analysis has determined the chemical composition of each prostatic calculus and the SEM observation has described the morphology of the calculi surfaces and layers. Infrared analysis revealed that 90.7% of the stones were mainly composed of calcium phosphates. However, several mineral phases previously not reported in prostatic calculi were observed, as brushite or octocalcium phosphate pentahydrate. CONCLUSION Prostatic calculi exhibited a diversity of crystalline composition and morphology. As previously reported for urinary calculi, relationships between composition and morphology of prostatic stones and étiopathogenic conditions could be of interest in clinical practice.

MOMAC: a SAXS/WAXS laboratory instrument dedicated to nanomaterials

This article presents the technical characteristics of a newly built small-and wide-angle X-ray scattering (SAXS/WAXS) apparatus dedicated to structural characterization of a wide range of nanomaterials in the powder or dispersion form. The instrument is based on a high-flux rotating anode generator with a molybdenum target, enabling the assessment of highly absorbing samples containing heavy elements. The SAXS part is composed of a collimation system including a multilayer optic and scatterless slits, a motorized sample holder, a vacuum chamber, and a two-dimensional image-plate detector. All the control command is done through a TANGO interface. Normalization and data correction yield scattering patterns at the absolute scale automatically with a q range from 0.03 to 3.2 A ˚ A1. The WAXS part features a multilayer collimating optic and a two-dimensional image-plate detector with variable sample-to-detector distances. The accessible q range is 0.4–9 A ˚ A1 , ensuring a large overlap in q range between the two instruments. A few examples of applications are also presented, namely coupled SAXS/WAXS structure and symmetry determination of gold nanocrystals in solution and characterization of imogolite nanotubes and iron-filled carbon nanotube samples.

Presence and role of trace elements in urinary calculi

AIM To assess the possible nature and role of trace elements in the pathogenesis of urinary stones. MATERIAL AND METHOD A series of 76 calculi from the East-Algerian region has been investigated through Fourier transform infrared spectroscopy for chemical analysis and X-ray fluorescence for detecting trace elements. RESULTS Among the detected trace elements, Zn, Sr, Pb, Cu, Rb and Se, only the first three had significant values. Overall, the calcium components, namely calcium oxalate and calcium phosphate, were the most loaded by these elements contrary to organic components such as uric acid and cystine, which had low contents. CONCLUSION The correlation of contents of Zn and Sr with the stone components (carbapatite, weddellite and whewellite) suggests an adsorption of these trace elements in the case of calcium stones rather than a catalytic process. LEVEL OF EVIDENCE 3.