Influence of ionic additives on triclinic calcium pyrophosphate dihydrate precipitation

Triclinic calcium pyrophosphate dihydrate (t- CPPD) crystals are one of the two polymorphs of microcrystals that have been found in the joints of patients suffering from pseudogout. However, there is currently no treatment for inhibiting the formation of these crystals, which present a high inflammatory potential. In this context we studied in vitro the precipitation of t-CPPD in a stirred reactor under pH- and temperature-controlled conditions and determined the effect of selected biologically relevant ionic additives (Mg2+, Cu2+, Fe3+, Zn2+, S2O3 2−) on its formation. The results showed that 1 mM Fe3+, Zn2+, or Cu2+ induced the most significant changes by partly inhibiting the crystallization of t-CPPD and favoring the formation of an amorphous-CPP phase (98 wt %) in the presence of Fe3+ or a monoclinic-CPPD phase (78 or 71 wt %, respectively) in the presence of Zn2+ or Cu2+. Correlations between 31P solid-state NMR, XRD, and elemental analyses showed that the additive cations are inserted into the monoclinic-CPPD and/or amorphous-CPP phases. This study, which combines structural, morphological, and elemental analyses, paves the way toward a deeper comprehension of the role of ionic additives in preventing the formation of CPPD crystalline phases, and is a key step in long-term development of an effective therapeutic treatmen

Microbobines et RMN en phase solide

National audienceThis PhD thesis, at the interface between chemistry and physics, uses Solid State Nuclear Magnetic Resonance (ssNMR) for both exploiting diversity of materials and developing new easy-to-implement methodologies.ssNMR has proved to be really efficient to study materials and especially their interface by precisely characterising chemical environment of studied nuclei [1]. However, the main drawback of this technique is its lack of sensitivity, each analysis requiring 30 to 400 mg of sample. Such an amount is particularly difficult to obtain for sol-gel thin-film layers or for biological studies like Kidney stones.In order to solve this issue, the MACS (Magic Angle Coil Spinning) technique has been recently developed [2]. It consists of a micro-scaled coil surrounding a capillary containing the sample. Only 30 to 100 µg of material is necessary. As the microcoil is placed inside the usual solid state NMR rotor, no probe modification is needed.[1] C. Bonhomme, C. Gervais, and D. Laurencin, “Recent NMR developments applied to organic–inorganic materials,”Progress in Nuclear Magnetic Resonance Spectroscopy, vol. 77, pp. 1–48, Feb. 2014.[2] D. Sakellariou, G. L. Goff, and J.-F. Jacquinot, “High-resolution, high-sensitivity NMR of nanolitre anisotropic samples by coil spinning,” Nature, vol. 447, no. 7145, pp. 694–697, Jul. 2007

From crystalline to amorphous calcium pyrophosphates:a solid state Nuclear Magnetic Resonance perspective

Hydrated calcium pyrophosphates (CPP, Ca2P2O7·nH2O) are a fundamental family of materials among osteoarticular pathologic calcifications. In this contribution, a comprehensive multinuclear NMR (Nuclear Magnetic Resonance) study of four crystalline and two amorphous phases of this family is presented. 1H, 31P and 43Ca MAS (Magic Angle Spinning) NMR spectra were recorded, leading to informative fingerprints characterizing each compound. In particular, different 1H and 43Ca solid state NMR signatures were observed for the amorphous phases, depending on the synthetic procedure used. The NMR parameters of the crystalline phases were determined using the GIPAW (Gauge Including Projected Augmented Wave) DFT approach, based on first-principles calculations. In some cases, relaxed structures were found to improve the agreement between experimental and calculated values, demonstrating the importance of proton positions and pyrophosphate local geometry in this particular NMR crystallography approach. Such calculations serve as a basis for the future ab initio modeling of the amorphous CPP phases. Statement of significance The general concept of NMR crystallography is applied to the detailed study of calcium pyrophosphates (CPP), whether hydrated or not, and whether crystalline or amorphous. CPP are a fundamental family of materials among osteoarticular pathologic calcifications. Their prevalence increases with age, impacting on 17.5% of the population after the age of 80. They are frequently involved or associated with acute articular arthritis such as pseudogout. Current treatments are mainly directed at relieving the symptoms of joint inflammation but not at inhibiting CPP formation nor at dissolving these crystals. The combination of advanced NMR techniques, modeling and DFT based calculation of NMR parameters allows new original insights in the detailed structural description of this important class of biomaterials

Multinuclear solid-state NMR investigation of Hexaniobate and Hexatantalate compounds

This work determines the potential of solid-state NMR techniques to probe proton, alkali, and niobium environments in Lindqvist salts. Na7HNb6O19·15H2O (1), K8Nb6O19·16H2O (2), and Na8Ta6O19·24.5H2O (3) have been studied by solid-state static and magic angle spinning (MAS) NMR at high and ultrahigh magnetic field (16.4 and 19.9 T). 1H MAS NMR was found to be a convenient and straightforward tool to discriminate between protonated and nonprotonated clusters AxH8–xM6O19·nH2O (A = alkali ion; M = Nb, Ta). 93Nb MAS NMR studies at different fields and MAS rotation frequencies have been performed on 1. For the first time, the contributions of NbO5Oμ2H sites were clearly distinguished from those assigned to NbO6 sites in the hexaniobate cluster. The strong broadening of the resonances obtained under MAS was interpreted by combining chemical shift anisotropy (CSA) with quadrupolar effects and by using extensive fitting of the line shapes. In order to obtain the highest accuracy for all NMR parameters (CSA and quadrupolar), 93Nb WURST QCPMG spectra in the static mode were recorded at 16.4 T for sample 1. The 93Nb NMR spectra were interpreted in connection with the XRD data available in the literature (i.e., fractional occupancies of the NbO5Oμ2H sites). 1D 23Na MAS and 2D 23Na 3QMAS NMR studies of 1 revealed several distinct sodium sites. The multiplicity of the sites was again compared to structural details previously obtained by single-crystal X-ray diffraction (XRD) studies. The 23Na MAS NMR study of 3 confirmed the presence of a much larger distribution of sodium sites in accordance with the 10 sodium sites predicted by XRD. Finally, the effect of Nb/Ta substitutions in 1 was also probed by multinuclear MAS NMR (1H, 23Na, and 93Nb)

Characterization of a 4H-SiC High Power Density Controlled Current Limiter

International audienceCritical steps for the fabrication of SiC devices are thermal annealing and metal ohmic contact formation. Metal annealing effect on the electrical characteristics of the current limiter underlines the necessity to control this device fabrication step. Measurements of contact resistivity as a function of temperature demonstrate the stability of the N type Ni/SiC contact in the range of 175 K-450 K as its value remains constant around 40 µΩ.cm 2. Post implantation annealing effect on the sheet resistance (Rsh) shows that a 1700°C/30 min annealing gives better trade off in terms of dopant activation and surface roughness. High power density has been measured up to 600 V. Current thermal stability has been measured for an applied drain to source voltage of 100 V and exhibits high power density capabilities of SiC VJFET as a controlled current limiter. Introduction

Generic magnetic field intensity profiles of interplanetary coronal mass ejections at Mercury, Venus and Earth from superposed epoch analyses

We study interplanetary coronal mass ejections (ICMEs) measured by probes at different heliocentric distances (0.3-1 AU) to investigate the propagation of ICMEs in the inner heliosphere and determine how the generic features of ICMEs change with heliospheric distance. Using data from the MErcury Surface, Space ENvironment, GEochemistry, and Ranging (MESSENGER), Venus Express and ACE spacecraft, we analyze with the superposed epoch technique the profiles of ICME substructures, namely, the sheath and the magnetic ejecta. We determine that the median magnetic field magnitude in the sheath correlates well with ICME speeds at 1 AU, and we use this proxy to order the ICMEs at all spacecraft. We then investigate the typical ICME profiles for three categories equivalent to slow, intermediate, and fast ICMEs. Contrary to fast ICMEs, slow ICMEs have a weaker solar wind field at the front and a more symmetric magnetic field profile. We find the asymmetry to be less pronounced at Earth than at Mercury, indicating a relaxation taking place as ICMEs propagate. We also find that the magnetic field intensities in the wake region of the ICMEs do not go back to the pre-ICME solar wind intensities, suggesting that the effects of ICMEs on the ambient solar wind last longer than the duration of the transient event. Such results provide an indication of physical processes that need to be reproduced by numerical simulations of ICME propagation. The samples studied here will be greatly improved by future missions dedicated to the exploration of the inner heliosphere, such as Parker Solar Probe and Solar Orbiter.Peer reviewe

Solid-state nuclear magnetic resonance: A valuable tool to explore organic-inorganic interfaces in silica-based hybrid materials

International audienc