Gas-phase reactions of carbon cluster ions with isomeric chloropropenes

Sun J, Grützmacher H-F, Lifshitz C. Gas-phase reactions of carbon cluster ions with isomeric chloropropenes. International Journal of Mass Spectrometry and Ion Processes. 1994;138:49-61.Gas-phase ion/molecule reactions of carbon cluster ions (C-n(.+), n = 10-20) with allylchloride (AC) and 2-chloro-propene (CP) were investigated by Fourier transform ion cyclotron resonance spectrometry (FT-ICR). The carbon cluster ions C-n(.+) were generated by electron impact ionization of perchloroarenes and subsequent elimination of all Cl substituents from the molecular ion giving rise to monocyclic C-n(.+). Clear pseudo-first-order reactions were observed for the carbon cluster ions C-n(.+) thus formed without any sign of isomeric clusters of different reactivity. An exception is C-11(.+), for which a small amount of unreactive ions was observed. The reactions of C-n(.+) with AC and CP at low operating pressure (1.2 x 10(-8)-8.0 x 10(-7) mbar) yield product ions Cn+3H5+ by loss of Cl from an intermediate adduct. Rate constants for the reactions with CP are always distinctly larger than with AC in spite of the smaller dissociation energy of the C-Cl bond in AC. Exceptionally large reaction efficiencies are found for C-13(.+) and C-17(.+), corroborating the high reactivity of cyclic anti-aromatic C-n(.+) with n = 4r + 1. The nature of the reaction products depends on the number of carbon atoms in C-n(.+). Secondary reactions of primary product ions Cn+3H5+ were observed only for reactions of odd numbered C-13(.+) and C-17(.+). Further, on collision induced dissociation (CID) the product ions from even C-n(.+) yield exclusively C3H3+, while product ions from odd C-n(.+) generate several fragment ions by loss of H and of C-(2-4)H-2. A reaction model explaining these observations is proposed

Radiogenic isotopes: Tracers of past ocean circulation and erosional input

The radiogenic isotope composition of dissolved trace metals in the ocean represents a set of relatively new and not yet fully exploited tracers with a large potential for oceanographic and paleoceanographic research on timescales from the present back to at least 60 Ma. The main topic of this review are those trace metals with oceanic residence times on the order of or shorter than the global mixing time of the ocean (Nd, Pb, Hf, and, in addition, Be). Their isotopic composition in the ocean has varied as a function of changes in paleocirculation, source provenances, style and intensity of weathering on the continents, as well as orogenic processes. The relative importance of these processes for each trace metal is evaluated, which is a prerequisite for reliable interpretation of their time series in terms of changes in paleocirculation or weathering inputs. This analysis of processes includes a discussion of the long-term isotopic evolution of Sr and Os, which are well mixed in the ocean and have thus not been influenced by circulation changes. The radiogenic isotope evolution of those trace metals with intermediate oceanic residence times can be used as paleoceanographic proxies to reconstruct paleocirculation and weathering inputs into the ocean. This is demonstrated by studies from different ocean basins, mainly carried out on ferromanganese crusts, which show that radiogenic trace metal isotopes provide important new insights and can complement results obtained by other well-established paleoceanographic tracers such as carbon isotopes

[3H]Adenine is a suitable radioligand for the labeling of G protein-coupled adenine receptors but shows high affinity to bacterial contaminations in buffer solutions

[3H]Adenine has previously been used to label the newly discovered G protein-coupled murine adenine receptors. Recent reports have questioned the suitability of [3H]adenine for adenine receptor binding studies because of curious results, e.g. high specific binding even in the absence of mammalian protein. In this study, we showed that specific [3H]adenine binding to various mammalian membrane preparations increased linearly with protein concentration. Furthermore, we found that Tris-buffer solutions typically used for radioligand binding studies (50 mM, pH 7.4) that have not been freshly prepared but stored at 4°C for some time may contain bacterial contaminations that exhibit high affinity binding for [3H]adenine. Specific binding is abolished by heating the contaminated buffer or filtering it through 0.2-μm filters. Three different, aerobic, gram-negative bacteria were isolated from a contaminated buffer solution and identified as Achromobacter xylosoxidans, A. denitrificans, and Acinetobacter lwoffii. A. xylosoxidans, a common bacterium that can cause nosocomial infections, showed a particularly high affinity for [3H]adenine in the low nanomolar range. Structure–activity relationships revealed that hypoxanthine also bound with high affinity to A. xylosoxidans, whereas other nucleobases (uracil, xanthine) and nucleosides (adenosine, uridine) did not. The nature of the labeled site in bacteria is not known, but preliminary results indicate that it may be a high-affinity purine transporter. We conclude that [3H]adenine is a well-suitable radioligand for adenine receptor binding studies but that bacterial contamination of the employed buffer solutions must be avoided

Orbital forcing of glacial/interglacial variations in chemical weathering and silicon cycling within the upper White Nile basin, East Africa: Stable-isotope and biomarker evidence from Lakes Victoria and Edward

On Quaternary time scales, the global biogeochemical cycle of silicon is interlocked with the carbon cycle through biotic enhancement of silicate weathering and uptake of dissolved silica by vascular plants and aquatic microalgae (notably diatoms, for which Si is an essential nutrient). Large tropical river systems dominate the export of Si from the continents to the oceans. Here, we investigate variations in Si cycling in the upper White Nile basin over the last 15 ka, using sediment cores from Lakes Victoria and Edward. Coupled measurements of stable O and Si isotopes on diatom separates were used to reconstruct past changes in lake hydrology and Si cycling, while the abundances of lipid biomarkers characteristic of terrestrial/emergent higher plants, submerged/floating aquatic macrophytes and freshwater algae document past ecosystem changes. During the late-glacial to mid-Holocene, 15–5.5 ka BP, orbital forcing greatly enhanced monsoon rainfall, forest cover and chemical weathering. Riverine inputs of dissolved silica from the lake catchments exceeded aquatic demand and may also have had lower Si-isotope values. Since 5.5 ka BP, increasingly dry climates and more open vegetation, reinforced by the spread of agricultural cropland over the last 3–4 ka, have reduced dissolved silica inputs into the lakes. Centennial-to millennial-scale dry episodes are also evident in the isotopic records and merit further investigation

A review of the stable isotope bio-geochemistry of the global silicon cycle and its associated trace elements

Silicon (Si) is the second most abundant element in the Earth’s crust and is an important nutrient in the ocean. The global Si cycle plays a critical role in regulating primary productivity and carbon cycling on the continents and in the oceans. Development of the analytical tools used to study the sources, sinks, and fluxes of the global Si cycle (e.g., elemental and stable isotope ratio data for Ge, Si, Zn, etc.) have recently led to major advances in our understanding of the mechanisms and processes that constrain the cycling of Si in the modern environment and in the past. Here, we provide background on the geochemical tools that are available for studying the Si cycle and highlight our current understanding of the marine, freshwater and terrestrial systems. We place emphasis on the geochemistry (e.g., Al/Si, Ge/Si, Zn/Si, d13C, d15N, d18O, d30Si) of dissolved and biogenic Si, present case studies, such as the Silicic Acid Leakage Hypothesis, and discuss challenges associated with the development of these environmental proxies for the global Si cycle. We also discuss how each system within the global Si cycle might change over time (i.e., sources, sinks, and processes) and the potential technical and conceptual limitations that need to be considered for future studies

Non-AIDS defining cancers in the D:A:D Study-time trends and predictors of survival : a cohort study

BACKGROUND:Non-AIDS defining cancers (NADC) are an important cause of morbidity and mortality in HIV-positive individuals. Using data from a large international cohort of HIV-positive individuals, we described the incidence of NADC from 2004-2010, and described subsequent mortality and predictors of these.METHODS:Individuals were followed from 1st January 2004/enrolment in study, until the earliest of a new NADC, 1st February 2010, death or six months after the patient's last visit. Incidence rates were estimated for each year of follow-up, overall and stratified by gender, age and mode of HIV acquisition. Cumulative risk of mortality following NADC diagnosis was summarised using Kaplan-Meier methods, with follow-up for these analyses from the date of NADC diagnosis until the patient's death, 1st February 2010 or 6 months after the patient's last visit. Factors associated with mortality following NADC diagnosis were identified using multivariable Cox proportional hazards regression.RESULTS:Over 176,775 person-years (PY), 880 (2.1%) patients developed a new NADC (incidence: 4.98/1000PY [95% confidence interval 4.65, 5.31]). Over a third of these patients (327, 37.2%) had died by 1st February 2010. Time trends for lung cancer, anal cancer and Hodgkin's lymphoma were broadly consistent. Kaplan-Meier cumulative mortality estimates at 1, 3 and 5 years after NADC diagnosis were 28.2% [95% CI 25.1-31.2], 42.0% [38.2-45.8] and 47.3% [42.4-52.2], respectively. Significant predictors of poorer survival after diagnosis of NADC were lung cancer (compared to other cancer types), male gender, non-white ethnicity, and smoking status. Later year of diagnosis and higher CD4 count at NADC diagnosis were associated with improved survival. The incidence of NADC remained stable over the period 2004-2010 in this large observational cohort.CONCLUSIONS:The prognosis after diagnosis of NADC, in particular lung cancer and disseminated cancer, is poor but has improved somewhat over time. Modifiable risk factors, such as smoking and low CD4 counts, were associated with mortality following a diagnosis of NADC

The Cannington Ag-Pb-Zn deposit Queensland, Australia and Aggeneys-Gamsberg Zn-Pb Ore District South Africa: Broken Hill-type birds of a feather?

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The Aggeneys-Gamsberg Zn-Pb Ore district, South Africa and Cannington Ag-Pb-Zn deposit Queensland Australia: Broken Hill-tye birds of a feather?

Please help us populate SUNScholar with the post print version of this article. It can be e-mailed to: [email protected]