A review of carbonatitic magmatism in the Paraná-Angola-Namibia (PAN) system.

Mesozoic to Cenozoic alkaline-carbonatitic complexes from southern Brazil, Angola and Namibia occur along main tectonic lineaments. In general, the alkaline-carbonatite complexes show intrusive/subintrusive, subcircular or oval shaped structures and are indicative of high upwelling energy. Processes of liquid immiscibility from trachytic-phonolitic liquids, starting from parental alkaline mafic magmas are believed to have generated carbonatitic liquids, as suggested by field relationships and geochemical characteristics. Ca-, Mg- and Fe-carbonatites are widespread even in the same complex. The occurrences comprise three main chronogroups, i.e. 1) Early Cretaceous (Eastern Paraguay; Brazil, Ponta Grossa Arch and Anitapolis; Angola and Namibia); 2) Late Cretaceous (Brazil , Ponta Grossa Arch, Lages and Alto Paranaiba. Namibia); 3) Paleogene, Brazil and Namibia Two principal types of associated alkaline rocks are represented, i.e. plagioleucitites l.s. (Eastern Paraguay; Brazil: Ponta Grossa Arch- Angola and Namibia) and kamafugites l.s. (Brazil: alto Paranaiba and Lages; Namibia). Significant variations in O-C isotope compositions are found in primary carbonates , the variations being mainly due to isotope exchange between carbonates and H2O-CO2-rich hydrothermal fluids, whereas magmatic processes, i.e. fractional crystallization or liquid immiscibility, probably affect the delta O-18 and delta C-13 values by not more than 2 delta%.. The isotope exchange model implies that the most significant isotopic variations took place in a hydrothermal environment, e.g. in the range 400-80 degrees C, involving fluids with CO2/H2O ratio ranging from 0.8 to 1. Sr-Nd-Pb isotope systematics highlight heterogeneous mixtures between HIMU and EMI mantle components, similar to the associated alkaline rocks and the flood tholeiites of the Parana-Angola-Etendeka (Namibia) system. This is also consistent with Re-Os systematics on selected mafic samples from the Alto Paranaiba alkaline-carbonatite province. The data relative to the noble gases suggest that the source(s) are similar to other mantle derived magmas (e.g. HIMU and MORB) and that the carbon of carbonatites is unlikely to be subduction-related carbon, and support a C-O fractionation model starting from mantle-derived sources. In spite of the strong variation shown by C-O isotopes, Sr-Nd-Pb-Os isotopic systematics could be related to an isotopically enriched source where the chemical heterogeneities reflect a depleted mantle "metasomatized" by small-volume melts and fluids rich in incompatible elements. These fluids are expected to have promoted crystallization in the mantle of K-rich phases that gave rise to a veined network variously enriched in LILE and LREE (cf. Foley, 1992b). The newly formed veins (enriched component) and peridotite matrix (depleted component) underwent a different isotopic evolution with time as reflected by the carbonatitic rocks. These conclusions may be extended to the whole Parana-Angola-Etendeka system, where isotopically distinct parent magmas were generated following two main enrichment events of the subcontinental lithospheric mantle at 2.0-1.4 and 1.0-0.5 Ga, respectively, as also supported by Re-Os systematics. The mantle sources preserved the isotopic heterogeneities over a long time, suggesting a non-convective lithospheric mantle beneath different cratons or intercratonic regions. Overall the data indicate that the alkaline-carbonatitic magmatism originated from a significant, but small scale heterogeneous subcontinental mantle. In this scenario, the Tristan da Cunha, Walvis Ridge-Rio Grande Rise and Vitoria-Trindade hotspot tracks might reflect the accomodation of stresses in the lithosphere during rifting, rather than continuous magmatic activity induced by mantle plumes beneath the moving lithosphere

4D flow imaging of the thoracic aorta: is there an added clinical value?

Four-dimensional (4D) flow MRI has emerged as a powerful non-invasive technique in cardiovascular imaging, enabling to analyse in vivo complex flow dynamics models by quantifying flow parameters and derived features. Deep knowledge of aortic flow dynamics is fundamental to better understand how abnormal flow patterns may promote or worsen vascular diseases. In the perspective of an increasingly personalized and preventive medicine, growing interest is focused on identifying those quantitative functional features which are early predictive markers of pathological evolution. The thoracic aorta and its spectrum of diseases, as the first area of application and development of 4D flow MRI and supported by an extensive experimental validation, represents the ideal model to introduce this technique into daily clinical practice. The purpose of this review is to describe the impact of 4D flow MRI in the assessment of the thoracic aorta and its most common affecting diseases, providing an overview of the actual clinical applications and describing the potential role of derived advanced hemodynamic measures in tailoring follow-up and treatment

Angular Forces Around Transition Metals in Biomolecules

Quantum-mechanical analysis based on an exact sum rule is used to extract an semiclassical angle-dependent energy function for transition metal ions in biomolecules. The angular dependence is simple but different from existing classical potentials. Comparison of predicted energies with a computer-generated database shows that the semiclassical energy function is remarkably accurate, and that its angular dependence is optimal.Comment: Tex file plus 4 postscript figure

Reductive Elimination of Alkylamines from Low-Valent, Alkylpalladium(II) Amido Complexes

This article discusses reductive elimination of alkylamines from low-valent, alkylpalladium(II) amido complexes

Electronic transport, structure, and energetics of endohedral Gd@C82 metallofullerenes

Electronic structure and transport properties of the fullerene C$_{82}$ and the metallofullerene Gd@C$_{82}$ are investigated with density functional theory and the Landauer-Buttiker formalism. The ground state structure of Gd@C$_{82}$ is found to have the Gd atom below the C-C bond on the C$_2$ molecular axis of C$_{82}$. Insertion of Gd into C$_{82}$ deforms the carbon chain in the vicinity of the Gd atoms. Significant overlap of the electron distribution is found between Gd and the C$_{82}$ cage, with the transferred Gd electron density localized mainly on the nearest carbon atoms. This charge localization reduces some of the conducting channels for the transport, causing a reduction in the conductivity of the Gd@C$_{82}$ species relative to the empty C$_{82}$ molecule. The electron transport across the metallofullerene is found to be insensitive to the spin state of the Gd atom.Comment: 13 pages, 7 figures, submitted Nano Let

Second-order grey-scale texture analysis of pleural ultrasound images to differentiate acute respiratory distress syndrome and cardiogenic pulmonary edema

Discriminating acute respiratory distress syndrome (ARDS) from acute cardiogenic pulmonary edema (CPE) may be challenging in critically ill patients. Aim of this study was to investigate if gray-level co-occurrence matrix (GLCM) analysis of lung ultrasound (LUS) images can differentiate ARDS from CPE. The study population consisted of critically ill patients admitted to intensive care unit (ICU) with acute respiratory failure and submitted to LUS and extravascular lung water monitoring, and of a healthy control group (HCG). A digital analysis of pleural line and subpleural space, based on the GLCM with second order statistical texture analysis, was tested. We prospectively evaluated 47 subjects: 16 with a clinical diagnosis of CPE, 8 of ARDS, and 23 healthy subjects. By comparing ARDS and CPE patients’ subgroups with HCG, the one-way ANOVA models found a statistical significance in 9 out of 11 GLCM textural features. Post-hoc pairwise comparisons found statistical significance within each matrix feature for ARDS vs. CPE and CPE vs. HCG (P ≤ 0.001 for all). For ARDS vs. HCG a statistical significance occurred only in two matrix features (correlation: P = 0.005; homogeneity: P = 0.048). The quantitative method proposed has shown high diagnostic accuracy in differentiating normal lung from ARDS or CPE, and good diagnostic accuracy in differentiating CPE and ARDS. Gray-level co-occurrence matrix analysis of LUS images has the potential to aid pulmonary edemas differential diagnosis

Small molecules targeted to the microtubule–Hec1 interaction inhibit cancer cell growth through microtubule stabilization

Highly expressed in cancer protein 1 (Hec1) is a subunit of the kinetochore (KT)-associated Ndc80 complex, which ensures proper segregation of sister chromatids at mitosis by mediating the interaction between KTs and microtubules (MTs). HEC1 mRNA and protein are highly expressed in many malignancies as part of a signature of chromosome instability. These properties render Hec1 a promising molecular target for developing therapeutic drugs that exert their anticancer activities by producing massive chromosome aneuploidy. A virtual screening study aimed at identifying small molecules able to bind at the Hec1–MT interaction domain identified one positive hit compound and two analogs of the hit with high cytotoxic, pro-apoptotic and anti-mitotic activities. The most cytotoxic analog (SM15) was shown to produce chromosome segregation defects in cancer cells by inhibiting the correction of erroneous KT–MT interactions. Live cell imaging of treated cells demonstrated that mitotic arrest and segregation abnormalities lead to cell death through mitotic catastrophe and that cell death occurred also from interphase. Importantly, SM15 was shown to be more effective in inducing apoptotic cell death in cancer cells as compared to normal ones and effectively reduced tumor growth in a mouse xenograft model. Mechanistically, cold-induced MT depolymerization experiments demonstrated a hyper-stabilization of both mitotic and interphase MTs. Molecular dynamics simulations corroborate this finding by showing that SM15 can bind the MT surface independently from Hec1 and acts as a stabilizer of both MTs and KT–MT interactions. Overall, our studies represent a clear proof of principle that MT-Hec1-interacting compounds may represent novel powerful anticancer agents