Nomenclature of the hydrotalcite supergroup: Natural layered double hydroxides

Layered double hydroxide (LDH) compounds are characterized by structures in which layers with a brucite-like structure carry a net positive charge, usually due to the partial substitution of trivalent octahedrally coordinated cations for divalent cations, giving a general layer formula [( M 2+ 1-x M 3+ x )(OH)2] x +. This positive charge is balanced by anions which are intercalated between the layers. Intercalated molecular water typically provides hydrogen bonding between the brucite layers. In addition to synthetic compounds, some of which have significant industrial applications, more than 40 mineral species conform to this description. Hydrotalcite, Mg6Al2(OH) 16[CO3]•4H2O, as the longest-known example, is the archetype of this supergroup of minerals. We review the history, chemistry, crystal structure, polytypic variation and status of all hydrotalcite-supergroup species reported to date. The dominant divalent cations, M 2+, that have been reported in hydrotalcite supergroup minerals are Mg, Ca, Mn, Fe, Ni, Cu and Zn; the dominant trivalent cations, M 3+, are Al, Mn, Fe, Co and Ni. The most common intercalated anions are (CO3)2-, (SO4)2- and Cl -; and OH-, S2- and [Sb(OH)6] - have also been reported. Some species contain intercalated cationic or neutral complexes such as [Na(H2O)6]+ or [MgSO4]0. We define eight groups within the supergroup on the basis of a combination of criteria. These are (1) the hydrotalcite group, with M 2+:M 3+ = 3:1 (layer spacing ∼7.8 Å); (2) the quintinite group, with M 2+:M 3+ = 2:1 (layer spacing ∼7.8 Å); (3) the fougèrite group, with M 2+ = Fe2+, M 3+ = Fe3+ in a range of ratios, and with O2- replacing OH- in the brucite module to maintain charge balance (layer spacing ∼7.8 Å); (4) the woodwardite group, with variable M 2+:M 3+ and interlayer [SO4] 2-, leading to an expanded layer spacing of ∼8.9 Å; (5) the cualstibite group, with interlayer [Sb(OH)6]- and a layer spacing of ∼9.7 Å; (6) the glaucocerinite group, with interlayer [SO4]2- as in the woodwardite group, and with additional interlayer H2O molecules that further expand the layer spacing to ∼11 Å; (7) the wermlandite group, with a layer spacing of ∼11 Å, in which cationic complexes occur with anions between the brucite-like layers; and (8) the hydrocalumite group, with M 2+ = Ca2+ and M 3+ = Al, which contains brucite-like layers in which the Ca:Al ratio is 2:1 and the large cation, Ca2+, is coordinated to a seventh ligand of 'interlayer' water. The principal mineral status changes are as follows. (1) The names manasseite, sjögrenite and barbertonite are discredited; these minerals are the 2H polytypes of hydrotalcite, pyroaurite and stichtite, respectively. Cyanophyllite is discredited as it is the 1M polytype of cualstibite. (2) The mineral formerly described as fougèrite has been found to be an intimate intergrowth of two phases with distinct Fe 2+:Fe3+ ratios. The phase with Fe2+:Fe 3+ = 2:1 retains the name fougèrite; that with Fe 2+:Fe3+ = 1:2 is defined as the new species trébeurdenite. (3) The new minerals omsite (IMA2012-025), Ni 2Fe3+(OH)6[Sb(OH)6], and mössbauerite (IMA2012-049), Fe3+ 6O 4(OH)8[CO3]•3H2O, which are both in the hydrotalcite supergroup are included in the discussion. (4) Jamborite, carrboydite, zincaluminite, motukoreaite, natroglaucocerinite, brugnatellite and muskoxite are identified as questionable species which need further investigation in order to verify their structure and composition. (5) The ranges of compositions currently ascribed to motukoreaite and muskoxite may each represent more than one species. The same applies to the approved species hydrowoodwardite and hydrocalumite. (6) Several unnamed minerals have been reported which are likely to represent additional species within the supergroup. This report has been approved by the Commission on New Minerals, Nomenclature and Classification (CNMNC) of the International Mineralogical Association, voting proposal 12-B. We also propose a compact notation for identifying synthetic LDH phases, for use by chemists as a preferred alternative to the current widespread misuse of mineral names. © 2012 Mineralogical Society.Fil: Mills, S.J.. Museum Victoria; AustraliaFil: Christy, A.G.. Australian National University. Centre for Advanced Microscopy; AustraliaFil: Génin, J. M. R.. CNRS-Université de Lorraine; FranciaFil: Kameda, T.. Tohoku University. Graduate School of Environmental Studies; JapónFil: Colombo, Fernando. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigaciones en Ciencias de la Tierra. Universidad Nacional de Córdoba. Facultad de Ciencias Exactas Físicas y Naturales. Centro de Investigaciones en Ciencias de la Tierra; Argentin

Comparison Of Structure And Properties Of Femtosecond And Nanosecond Laser-Structured Silicon

We compare the optical properties,chemical composition, and crystallinity of siliconmicrostructures formed in the presence of SF6 by femtosecond laserirradiation and by nanosecond laser irradiation. In spite of very different morphology and crystallinity, the optical properties and chemical composition of the two types of microstructures are very similar. The structures formed with femtosecond (fs) pulses are covered with a disordered nanocrystalline surface layer less than 1 μm thick, while those formed with nanosecond (ns) pulses have very little disorder. Both ns-laser-formed and fs-laser-formed structures absorb near-infrared (1.1–2.5 μm) radiation strongly and have roughly 0.5% sulfur impurities

Advances in the numerical treatment of grain-boundary migration: Coupling with mass transport and mechanics

This work is based upon a coupled, lattice-based continuum formulation that was previously applied to problems involving strong coupling between mechanics and mass transport; e.g. diffusional creep and electromigration. Here we discuss an enhancement of this formulation to account for migrating grain boundaries. The level set method is used to model grain-boundary migration in an Eulerian framework where a grain boundary is represented as the zero level set of an evolving higher-dimensional function. This approach can easily be generalized to model other problems involving migrating interfaces; e.g. void evolution and free-surface morphology evolution. The level-set equation is recast in a remarkably simple form which obviates the need for spatial stabilization techniques. This simplified level-set formulation makes use of velocity extension and field re-initialization techniques. In addition, a least-squares smoothing technique is used to compute the local curvature of a grain boundary directly from the level-set field without resorting to higher-order interpolation. A notable feature is that the coupling between mass transport, mechanics and grain-boundary migration is fully accounted for. The complexities associated with this coupling are highlighted and the operator-split algorithm used to solve the coupled equations is described.Comment: 28 pages, 9 figures, LaTeX; Accepted for publication in Computer Methods in Applied Mechanics and Engineering. [Style and formatting modifications made, references added.

The reduction of chromate ions by Fe(II) layered hydroxides

International audienceThe reduction of chromate ions by Fe(OH)2 and the iron (II)-iron (III) hydroxysulphate green rust, GR(SO42-), was studied to evaluate whether such synthetic layered hydroxides and the corresponding natural green rust mineral could be involved in the natural attenuation of contaminated environments. The resulting Cr (III) bearing phases, which would govern the subsequent behaviour of chromium, were clearly characterised. Both compounds proved to be very reactive and oxidised instantaneously while chromate ions were reduced to Cr (III) as evidenced by X-ray photoelectron spectroscopy. Mass balance (ICP-AES) demonstrated that the Fe/Cr ratio inside the solid end product was equal to the initial Fe/Cr ratio. The solid phases, analysed by X-ray diffraction, Raman and Mossbauer spectroscopies were identified as Cr-substituted poorly crystallised iron (III) oxyhydroxides in both cases, more precisely d-FeOOH when starting with Fe(OH)2 and ferrihydrite when starting with GR(SO42-)

Effect of Electric Field Distribution on the Morphologies of Laser-Induced Damage in Hafnia-Silica Multilayer Polarizers

Hafnia-silica multilayer polarizers were deposited by e-beam evaporation onto BK7 glass substrates. The polarizers were designed to operate at 1064 nm at Brewster`s angle (56{degree}). They were tested with a 3-ns laser pulse at 45, 56, and 65{degree} incidence angle in order to vary the electric field distribution in the multilayer, study their effects on damage morphology, and investigate possible advantages of off-use angle laser conditioning. Morphology of the laser-induced damage was characterized by optical and scanning electron microscopy. Four distinct damage morphologies (pit, flat bottom pit, scald, outer layer delamination) were observed; they depend strongly on incident angle of the laser beam. Massive delamination observed at 45 and 56{degree} incidence, did not occur at 65{degree}; instead, large and deep pits were found at 65{degree}. Electric field distribution, temperature rise, and change in stress in the multilayer were calculated to attempt to better understand the relation between damage morphology, electric field peak locations, and maximum thermal stress gradients. The calculations showed a twofold increase in stress change in the hafnia top layers depending on incident angle. Stress gradient in the first hafnia-silica interface was found to be highest for 45, 56, and 65{degree}, respectively. Finally, the maximum stress was deeper in the multilayer at 65{degree}. Although the limitations of such simple thermal mechanical model are obvious, the results can explain that outer layer delamination is more likely at 45 and 56{degree} than 65{degree} and that damage sites are expected to be deeper at 65{degree}

Mise à jour 2014 des recommandations du GEFPICS pour l’évaluation du statut HER2 dans les cancers du sein en France

De nouvelles recommandations internationales pour l’évaluation du statut HER2 dans les cancers du sein, basées sur plus de dix ans d’expérience et sur les résultats d’études cliniques et de concordance entre les différentes techniques de détection, viennent tout juste de voir le jour. Le présent article a pour objet de faire le point sur ces nouvelles recommandations, à la lumière de la publication récente du groupe de travail de l’American Society of Clinical Oncology (ASCO) et du Collège des pathologistes américains (CAP), adaptées à la pratique de la pathologie en France et revues par le groupe GEFPICS. À l’ère de la médecine personnalisée, la détermination du statut HER2 reste un élément phare dans le panel des biomarqueurs théranostiques des cancers du sein. Si l’interprétation du statut HER2 dans les cancers du sein est aisée dans la majorité des cas, un certain nombre de situations anatomocliniques est d’interprétation plus délicate, telles que la possibilité rare mais réelle de l’hétérogénéité intra-tumorale du statut de HER2, les formes à différenciation micropapillaire ou la ré-évaluation du statut des biomarqueurs lors de la rechute métastatique. Ces nouvelles recommandations abordent ces différentes questions, reprécisent les conditions pré-analytiques optimales et les critères d’interprétation (notamment des cas 2+), afin de réduire au maximum le risque de faux négatifs. Plus que jamais, la mobilisation de la spécialité d’anatomo-cytopathologie autour de la qualité des tests théranostiques témoigne de son implication dans la chaîne des soins en cancérologie., Summary International guidelines on HER2 determination in breast cancer have just been updated by the American Society of Clinical Oncology (ASCO) and College of American Pathologists (CAP), on the basis of more than ten-year practice, results of clinical trials and concordance studies. The GEFPICS group, composed of expert pathologists in breast cancer, herein presents these recommendations, adapted to the French routine practice. These guidelines highlight the possible diagnosis difficulties with regards to HER2 status determination, such as intra-tumor heterogeneity, special histological subtypes and biomarker re-evaluation during metastatic relapse. Pre-analytical issues and updated scoring criteria (especially for equivocal cases) are detailed, in order to decrease the occurrence of false negative cases. In the era of personalized medicine, pathologists are more than ever involved in the quality of oncotheranostic biomarker evaluation.

Mise à jour des recommandations du GEFPICS pour l’évaluation du statut HER2 dans les cancers du sein en France

En Europe, les patientes atteintes d’un cancer du sein invasif susceptibles de recevoir un traitement ciblé anti-HER2 sont actuellement sélectionnées sur la base d’un test immunohistochimique (IHC). Les techniques d’hybridation in situ (HIS) doivent être utilisées pour l’évaluation des cas IHC ambigus (2+) et pour l’étalonnage de la technique IHC. Les patientes éligibles au traitement ciblant HER2 présentent un statut HER2 positif défini par un test IHC 3+ ou un test 2+ amplifié. Une détection correcte du statut HER2 est indispensable à une utilisation optimale des thérapeutiques ciblées puisque leur efficacité est limitée aux patientes surexprimant HER2. Il est capital que l’évaluation du statut HER2 soit optimisée et fiable. Ces recommandations du groupe d’étude des facteurs pronostiques IHC dans le cancer du sein (GEFPICS) détaillent et commentent les différentes étapes des techniques IHC et HIS, les contrôles utilisables et les règles générales de l’apprentissage de la lecture. Une fois acquis, ce savoir-faire doit être pérennisé par l’observation de règles de bonnes pratiques techniques (utilisation rigoureuse de témoins internes et externes et participation régulière à des programmes d’Assurance qualité [AQ])., Summary In Europe, patients who may benefit from an HER2 targeted drug are currently selected by immunohistochemistry (IHC). In situ hybridization (ISH) techniques should be used for complementary assessment of ambiguous 2+ IHC cases and for the calibration of the IHC technique. Eligibility to an HER2 target treatment is defined by an HER2 positive status being IHC test 3+ or 2+ amplified. Reliable detection of HER2 status is essential to the appropriate usage of HER2 targeted drugs because its specificity is limited to tumors overexpressing HER2. It is essential that the IHC evaluation of the HER2 status of a mammary carcinoma is optimized and reliable. This GEFPICS’ guidelines look over the different steps of the IHC technique, the controls and, the rules for interpretation. Once acquired, this knowledge must be perpetuated by the observation of rules of good technical practice (internal and external controls, quality assurance programs)

Recommandations du GEFPICS concernant la phase pré-analytique pour l’évaluation de HER2 et des récepteurs hormonaux dans le cancer du sein : mise à jour 2014

Les tumeurs fixées et incluses en paraffine sont quotidiennement utilisées pour l’évaluation des biomarqueurs nécessaires au traitement des patientes atteintes d’un cancer du sein invasif. Les nouvelles recommandations internationales sur la phase pré-analytique ont été récemment revues, confirmant l’importance de la prise en charge optimale des prélèvements pour garantir des tests d’immunohistochimie ou d’hybridation in situ de qualité, quel que soit le biomarqueur envisagé. Incluant les procédés de fixation et de préparation des tissus, toutes les procédures pré-analytiques doivent être validées, standardisées et tracées. Elles nécessitent la collaboration et la formation de toutes les personnes impliquées dans le circuit du prélèvement, du préleveur jusqu’au technicien de pathologie et au pathologiste en passant par l’infirmière, ou le coursier. La prise en charge initiale optimale des pièces et une fixation de qualité sont des étapes majeures à maîtriser dans la phase pré-analytique. Cette mise à jour des recommandations du groupe d’étude des facteurs pronostiques immunohistochimiques dans le cancer du sein (GEFPICS) détaille et commente les différentes étapes pré-analytiques. L’observation de ces règles de bonne pratique, l’utilisation rigoureuse de témoins internes et externes et la participation régulière à des programmes d’assurance qualité sont autant de garanties pour une évaluation correcte et pérenne des biomarqueurs oncothéranostiques., Summary Biomarker assessment of breast cancer tumor samples is part of the routine workflow of pathology laboratories. International guidelines have recently been updated, with special regards to the pre-analytical steps that are critical for the quality of immunohistochemical and in situ hybridization procedures, whatever the biomarker analyzed. Fixation and specimen handling protocols must be standardized, validated and carefully tracked. Cooperation and training of the personnel involved in the specimen workflow (e.g. radiologists, surgeons, nurses, technicians and pathologists) are of paramount importance. The GEFPICS’ update of the recommendations herein details and comments the different steps of the pre-analytical process. Application of these guidelines and participation to quality insurance programs are mandatory to ensure the correct evaluation of oncotheranostic biomarkers