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

Acoustics for underwater neutrino telescopes

En esta tesis se tratan diferentes aspectos de la acústica presente en un telescopio submarino de neutrinos, principalmente en dos vertientes: en el sistema de posicionamiento acústico utilizado para la monitorización de las posiciones de los módulos ópticos presentes a lo largo del detector, así como en sistemas para detección acústica de neutrinos, técnica que actualmente está en fase de estudio. Todos los estudios realizados están enmarcados dentro de dos colaboraciones europeas para el diseño, construcción y operación de telescopios submarinos de neutrinos: Antares (en fase de operación) y KM3NET (en fase de diseño). Objetivos. Los objetivos de este trabajo pueden resumirse en los siguientes aspectos: - Estudios y análisis del sistema de posicionamiento acústico de Antares. Desarrollo del software para la para la automatización del procesado de los datos de dicho sistema e incorporación de los resultados en la base de datos del experimento. Análisis de los datos proporcionados por dicho sistema con el fin de validar su correcto funcionamiento. - Diseño y desarrollo del sistema de posicionamiento acústico para KM3NeT, telescopio unas 20 veces más grande que Antares. - Estudios para la evaluación de la generación acústica paramétrica para el desarrollo de un calibrador compacto capaz de generar señales tipo neutrino útiles en sistemas de detección acústica. Elementos de la metodología a destacar. Cabe destacar aquí que el trabajo se ha desarrollado en el marco de dos colaboraciones internacionales: ANTARES y KM3NeT, financiados con fondos europeos y nacionales. Por su contexto y el carácter de las actividades realizadas ha sido necesaria la formación en distintos campos: telescopios de neutrinos y astropartículas, pero también en otras áreas como la acústica submarina. Además, se ha desarrollado diversas capacidades y destrezas en diversos ámbitos: en instrumentación, en aplicaciones informáticas, en análisis de datos, etc. Más concretamente, se ha trabajado en aplicaciones informáticas para los desarrollos y análisis en ANTARES.Bou Cabo, M. (2011). Acoustics for underwater neutrino telescopes [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/10989Palanci

Sensitivity of the Cherenkov Telescope Array to TeV photon emission from the Large Magellanic Cloud

A deep survey of the Large Magellanic Cloud at ∼0.1-100 TeV photon energies with the Cherenkov Telescope Array is planned. We assess the detection prospects based on a model for the emission of the galaxy, comprising the four known TeV emitters, mock populations of sources, and interstellar emission on galactic scales. We also assess the detectability of 30 Doradus and SN 1987A, and the constraints that can be derived on the nature of dark matter. The survey will allow for fine spectral studies of N 157B, N 132D, LMC P3, and 30 Doradus C, and half a dozen other sources should be revealed, mainly pulsar-powered objects. The remnant from SN 1987A could be detected if it produces cosmic-ray nuclei with a flat power-law spectrum at high energies, or with a steeper index 2.3-2.4 pending a flux increase by a factor of >3-4 over ∼2015-2035. Large-scale interstellar emission remains mostly out of reach of the survey if its >10 GeV spectrum has a soft photon index ∼2.7, but degree-scale 0.1-10 TeV pion-decay emission could be detected if the cosmic-ray spectrum hardens above >100 GeV. The 30 Doradus star-forming region is detectable if acceleration efficiency is on the order of 1−10 per cent of the mechanical luminosity and diffusion is suppressed by two orders of magnitude within <100 pc. Finally, the survey could probe the canonical velocity-averaged cross-section for self-annihilation of weakly interacting massive particles for cuspy Navarro-Frenk-White profiles

Solid state NMR of tin containing compounds

A recent development in chemical research has been concerned with molecular assemblies, and all manner of structural aggregates, leading to the relatively new area of supramolecular chemistry. The systems under study are organometallic ion exchangers where the structural motif is [(Me(_3)Sn(^IV))(_4)M(^II)(CN)(_6)]=(_oo) (M=Fe, Ru, Os...). These 3D cyanides are not simply molecular crystals, and their chemistry and topology are more reminiscent of inorganic solids. By replacing the bridging unit (Me(_3)Sn(^IV)) with guests such as (nPr)(_4)N(^+) and (nBu)(_4)N(^+), new 3D structures can be engineered, leading to new compounds. Tin units show unchanged trigonal bypyramidal coordination upon variation of metal (M), guest size, hindrance by the ligands. Changes in the metal affect mainly the isotropic and anisotropic (^119)Sn shielding parameters. The interplay of the electronic nature of the metal(s) and the bonding capacity of the ligands is studied by (^59)Co NMR. Quadrupolar coupling constants and asymmetry parameters show how the coordinative bond is sensitive to spatial reorganisation. Shielding calculations for the [Me(_3)Sn(CN)(_2)]’ model and for different X-ray structures have been performed to reproduce trends in chemical shift changes. Relativity effects have been omitted from the computations. This approach had four major aims: (a) to establish the extent to which (^119)Sn isotropic chemical shifts can be computed by DPT methods with acceptable basis sets for model molecular fragments relevant to four selected compounds; (b) the computation of the U^Sn isotropic chemical shifts for different coordination geometries of the CN ligands; (c) the attempt to correlate between computed and observed isotropic chemical shifts for four selected compounds; (d) to ascertain whether such a correlation can be used to establish the assignment of three experimental (^119)Sn shifts in a predictive fashion

2012 Activity Report of the Regional Research Programme on Hadrontherapy for the ETOILE Center

2012 is the penultimate year of financial support by the CPER 2007-2013 for ETOILE's research program, sustained by the PRRH at the University Claude Bernard. As with each edition we make the annual review of the research in this group, so active for over 12 years now. Over the difficulties in the decision-making process for the implementation of the ETOILE Center, towards which all our efforts are focussed, some "themes" (work packages) were strengthened, others have progressed, or have been dropped. This is the case of the eighth theme (technological developments), centered around the technology for rotative beam distribution heads (gantries) and, after being synchronized with the developments of ULICE's WP6, remained so by ceasing its activities, coinciding also with the retirement of its historic leader at IPNL, Marcel Bajard. Topic number 5 ("In silico simulations") has suffered the departure of its leader, Benjamin Ribba, although the work has still been provided by Branka Bernard, a former postdoctoral fellow in Lyon Sud, and now back home in Croatia, still in contract with UCBL for the ULICE project. Aside from these two issues (and the fact that the theme "Medico-economical simulations" is now directly linked to the first one ("Medical Project"), the rest of the teams are growing, as evidenced by the publication statistics at the beginning of this report. This is obviously due to the financial support of our always faithful regional institutions, but also to the synergy that the previous years, the European projects, the arrival of the PRIMES LabEx, and the national France Hadron infrastructure have managed to impulse. The Rhone-Alpes hadron team, which naturally includes the researchers of LPC at Clermont, should also see its influence result in a strong presence in France Hadron's regional node, which is being organized. The future of this regional research is not yet fully guaranteed, especially in the still uncertain context of ETOILE, but the tracks are beginning to emerge to allow past and present efforts translate into a long future that we all want to see established. Each of the researchers in PRRH is aware that 2013 will be (and already is) the year of great challenge : for ETOILE, for the PRRH, for hadron therapy in France, for French hadrontherapy in Europe (after the opening and beginning of treatments in the German [HIT Heidelberg, Marburg], Italian [CNAO, Pavia] and Austrian [MedAustron, Wien Neuerstadt]) centers. Let us meet again in early 2014 for a comprehensive review of the past and a perspective for the future ..