176 research outputs found

    Frontal and Lateral Submarine Lobe Fringes: Comparing Sedimentary Facies, Architecture and Flow Processes

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    Submarine lobe fringe deposits form heterolithic successions that may include a high proportion of hybrid beds. The identification of lobe fringe successions aids interpretation of paleogeographic setting and the degree of basin confinement. Here, for the first time, the sedimentological and architectural differences between frontal and lateral lobe fringe deposits are investigated. Extensive outcrop and core data from Fan 4, Skoorsteenberg Formation, Karoo Basin, South Africa, allow the rates and style of facies changes from axis to fringe settings of lobes and lobe complexes in both down-dip (frontal) and across-strike (lateral) directions to be tightly constrained over a 800 km2 study area. Fan 4 comprises three sand-prone divisions that form compensationally stacked lobe complexes, separated by thick packages of thin-bedded siltstone and sandstone intercalated with (muddy) siltstone, interpreted as the fringes of lobe complexes. Lobe-fringe facies associations comprise: i) thick-bedded structureless or planar laminated sandstones that pinch and swell, and are associated with underlying debrites; ii) argillaceous and mudclast-rich hybrid beds; and iii) current ripple-laminated sandstones and siltstones. Typically, frontal fringes contain high proportions of hybrid beds and transition from thick-bedded sandstones over length-scales of 1 to 2 km. In contrast, lateral fringe deposits tend to comprise current ripple-laminated sandstones that transition to thick-bedded sandstones in the lobe axis over several kilometers. Variability of primary flow processes are interpreted to control the documented differences in facies association. Preferential deposition of hybrid beds in frontal fringe positions is related to the dominantly downstream momentum of the high-density core of the flow. In contrast, the ripple-laminated thin beds in lateral fringe positions are interpreted to be deposited by more dilute low-density (parts of the) flows. The development of recognition criteria to distinguish between frontal and lateral lobe fringe successions is critical to improving paleogeographic reconstructions of submarine fans at outcrop and in the subsurface, and will help to reduce uncertainty during hydrocarbon field appraisal and development

    Perceptions and Practices in School Social Worker-Teacher Interprofessional Collaboration

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    School social work requires significant skills for interprofessional collaboration, especially collaboration with teachers. While the value of such skills is increasingly recognized in fields such as healthcare, there has been limited attention to assessing or supporting interprofessional practice in education. This exploratory mixed-methods study analyzed survey data from 264 school social workers across the United States in order to understand their perceptions of teachers as collaborators and their practices relating to collaboration with teachers. Barriers to collaboration were also identified. Data suggested that school social workers had positive perceptions of teachers as collaborators generally, but saw limitations in the training and support of teachers to effectively respond to non-academic concerns; time and support for collaboration were identified as significant barriers to collaborative practice

    Nucleophile-Catalyzed Additions to Activated Triple Bonds. Protection of Lactams, Imides, and Nucleosides with MocVinyl and Related Groups

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    Additions of lactams, imides, (S)-4-benzyl-1,3-oxazolidin-2-one, 2-pyridone, pyrimidine-2,4-diones (AZT derivatives), or inosines to the electron-deficient triple bonds of methyl propynoate, tert-butyl propynoate, 3-butyn-2-one, N-propynoylmorpholine, or N-methoxy-N-methylpropynamide in the presence of many potential catalysts were examined. DABCO and, second, DMAP appeared to be the best (highest reaction rates and E/Z ratios), while RuCl3, RuClCp*(PPh3)2, AuCl, AuCl(PPh3), CuI, and Cu2(OTf)2 were incapable of catalyzing such additions. The groups incorporated (for example, the 2-(methoxycarbonyl)ethenyl group that we name MocVinyl) serve as protecting groups for the above-mentioned heterocyclic CONH or CONHCO moieties. Deprotections were accomplished via exchange with good nucleophiles: the 1-dodecanethiolate anion turned out to be the most general and efficient reagent, but in some particular cases other nucleophiles also worked (e.g., MocVinyl-inosines can be cleaved with succinimide anion). Some structural and mechanistic details have been accounted for with the help of DFT and MP2 calculations

    Anatomy of an exhumed debrite and impact on stratal architecture

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    Submarine debrites generate complicated patterns of seabed relief which in uence subsequent ow behaviour and depositional patterns. However, recognizing this interaction in subsurface data is challenging in seismic and well data. To bridge this resolution gap, large-scale outcrop analogues can be used. The early post-rift Middle Jurassic succession of the Los Molles Formation is well-exposed along a 10 km long and downdip-orientated W-E outcrop belt located the western Central Neuquen Basin, Argentina.Fil: Martanez Donate, Ander. University of Manchester; Reino UnidoFil: Privat, Aurelia. University of Leeds; Reino UnidoFil: Spychala, Yvonne. Leibniz Universitat Hannover; AlemaniaFil: Hodgson, David. University of Leeds; Reino UnidoFil: Jackson, Christopher A. L.. Imperial College London; Reino UnidoFil: Kane, Ian. University of Manchester; Reino UnidoFil: Schwarz, Ernesto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigaciones Geológicas. Universidad Nacional de La Plata. Facultad de Ciencias Naturales y Museo. Centro de Investigaciones Geológicas; ArgentinaFil: Flint, Stephen S.. University of Manchester; Reino Unido59th British Sedimentological Research Group Annual General MeetingLiverpoolReino UnidoBritish Sedimentological Research GroupUniversity of Liverpoo

    Development and testing of a novel sulfur dioxide sonde

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    A novel technique has been developed to measure sulfur dioxide (SO2) using a modification of the existing electrochemical concentration cell (ECC) ozonesonde technology. The current sonde-based method to measure SO2 (i.e., the dual-sonde approach) involves launching two ozonesondes together, with one of the sondes having a filter to remove SO2 at the inlet. The SO2 profile is determined by taking the difference between the measurements from the two instruments. The dual-sonde method works well in typical tropospheric conditions when [O3]&gt;[SO2] but saturates when [SO2]&gt;[O3] and has large uncertainties in the upper troposphere and lower stratosphere that would limit its effectiveness in measuring SO2 from an explosive volcanic eruption. Due to these limitations, several modifications were made to create a single-sonde system that would directly measure SO2 (i.e., the SO2 sonde). These modifications included (1) a positively biased ECC current, (2) the addition of an O3 removal filter, and (3) the addition of a sample dryer. The SO2 sonde measures SO2 as a reduction in the cell current. There was a strong correlation (r2&gt;0.94) between the SO2 sonde and a Thermo 43c analyzer during controlled laboratory tests and pre-flight tests. Varying humidity levels affected the SO2 sonde's sensitivity (avg =84.6±31.7 ppbv µA−1, 1σ RSD =37 %) during initial field tests, which was resolved by adding a sample dryer upstream of the O3 removal filter and pump inlet. This modification significantly reduced the variability and increased the sensitivity of the SO2 measurements (avg =47±5.8 ppbv µA−1, 1σ RSD =12 %). Field tests included measurements near Kīlauea volcano (before and during the 2018 eruption of the Lower East Rift Zone), Costa Rica's Turrialba volcano, and anthropogenic plumes from the Athabasca oil sands region of Alberta, Canada. This single-SO2-sonde system is an effective, inexpensive instrument for measuring both ground-based and vertical profiles of SO2 from anthropogenic and natural sources (i.e., volcanic eruptions) over a wide range of concentrations.</p

    Synthesis of dicationic diarylpyridines as nucleic-acid binding agents

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    The syntheses of 2,6-bis[4-(4,5-dihydro-1H-imidazol-2-yl)phenyl]pyridine 7, 2-[4-(4,5-dihydro-1H-imidazol-2-yl)-phenyl]-6-[3-(4,5-dihydro-1H-imidazol-2-yl)phenyl]pyridine 8 and 2,6-bis[3-(4,5-dihydro-1H-imidazol-2-yl)phenyl]pyridine 9 in five steps from the appropriately substituted bromoacetophenone are described. 3,5-Bis[4-(4,5-dihydro-1H-imidazol-2-yl)phenyl]pyridine 13 is also reported, prepared in four steps from 4-bromophenylacetonitrile. The preparation of 2,5-bis[4-(4,5-dihydro-1H-imidazol-2-yl)-phenyl]pyridine 18 from 4-bromoacetophenone in six steps is presented. The dications bind to poly dA·dT in the order 7 > 13 > 18 > 8 > 9; the order of binding to poly A·U is 7 > 13 > 8 > 9; 18 essentially does not bind to the RNA model. Only 7 inhibits topoisomerase II at millimolar concentrations. The dicationic compounds that were tested against Pneumonocystis carinii in the immuno-suppressed rat model show only modest activity and are moderately toxic. Some of the compounds demonstrated modest anti-HIV-1 activity and selectivity in primary lymphocytes

    Late Effects After Haematopoietic Stem Cell Transplantation in ALL, Long-Term Follow-Up and Transition: A Step Into Adult Life

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    Haematopoietic stem cell transplant (HSCT) can be a curative treatment for children and adolescents with very-high-risk acute lymphoblastic leukaemia (ALL). Improvements in supportive care and transplant techniques have led to increasing numbers of long-term survivors worldwide. However, conditioning regimens as well as transplant-related complications are associated with severe sequelae, impacting patients' quality of life. It is widely recognised that paediatric HSCT survivors must have timely access to life-long care and surveillance in order to prevent, ameliorate and manage all possible adverse late effects of HSCT. This is fundamentally important because it can both prevent ill health and optimise the quality and experience of survival following HSCT. Furthermore, it reduces the impact of preventable chronic illness on already under-resourced health services. In addition to late effects, survivors of paediatric ALL also have to deal with unique challenges associated with transition to adult services. In this review, we: (1) provide an overview of the potential late effects following HSCT for ALL in childhood and adolescence; (2) focus on the unique challenges of transition from paediatric care to adult services; and (3) provide a framework for long-term surveillance and medical care for survivors of paediatric ALL who have undergone HSCT

    Structural Insights into the Inhibition of Cytosolic 5′-Nucleotidase II (cN-II) by Ribonucleoside 5′-Monophosphate Analogues

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    Cytosolic 5′-nucleotidase II (cN-II) regulates the intracellular nucleotide pools within the cell by catalyzing the dephosphorylation of 6-hydroxypurine nucleoside 5′-monophosphates. Beside this physiological function, high level of cN-II expression is correlated with abnormal patient outcome when treated with cytotoxic nucleoside analogues. To identify its specific role in the resistance phenomenon observed during cancer therapy, we screened a particular class of chemical compounds, namely ribonucleoside phosphonates to predict them as potential cN-II inhibitors. These compounds incorporate a chemically and enzymatically stable phosphorus-carbon linkage instead of a regular phosphoester bond. Amongst them, six compounds were predicted as better ligands than the natural substrate of cN-II, inosine 5′-monophosphate (IMP). The study of purine and pyrimidine containing analogues and the introduction of chemical modifications within the phosphonate chain has allowed us to define general rules governing the theoretical affinity of such ligands. The binding strength of these compounds was scrutinized in silico and explained by an impressive number of van der Waals contacts, highlighting the decisive role of three cN-II residues that are Phe 157, His 209 and Tyr 210. Docking predictions were confirmed by experimental measurements of the nucleotidase activity in the presence of the three best available phosphonate analogues. These compounds were shown to induce a total inhibition of the cN-II activity at 2 mM. Altogether, this study emphasizes the importance of the non-hydrolysable phosphonate bond in the design of new competitive cN-II inhibitors and the crucial hydrophobic stacking promoted by three protein residues

    A Review of Acute and Long-Term Neurological Complications Following Haematopoietic Stem Cell Transplant for Paediatric Acute Lymphoblastic Leukaemia

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    Despite advances in haematopoietic stem cell transplant (HSCT) techniques, the risk of serious side effects and complications still exists. Neurological complications, both acute and long term, are common following HSCT and contribute to significant morbidity and mortality. The aetiology of neurotoxicity includes infections and a wide variety of non-infectious causes such as drug toxicities, metabolic abnormalities, irradiation, vascular and immunologic events and the leukaemia itself. The majority of the literature on this subject is focussed on adults. The impact of the combination of neurotoxic drugs given before and during HSCT, radiotherapy and neurological complications on the developing and vulnerable paediatric and adolescent brain remains unclear. Moreover, the age-related sensitivity of the nervous system to toxic insults is still being investigated. In this article, we review current evidence regarding neurotoxicity following HSCT for acute lymphoblastic leukaemia in childhood. We focus on acute and long-term impacts. Understanding the aetiology and long-term sequelae of neurological complications in children is particularly important in the current era of immunotherapy for acute lymphoblastic leukaemia (such as chimeric antigen receptor T cells and bi-specific T-cell engager antibodies), which have well-known and common neurological side effects and may represent a future treatment modality for at least a fraction of HSCT-recipients
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