Kinetic and Spectroscopic Characterisation of Highly Reactive Methanesulfonates. Leaving Group Effects for Solvolyses and Comments on Geminal Electronic Effects Influencing SN_N1 Reactivity

Highly reactive methanesulfonates (mesylates, ROMs) have been prepared from 1-phenylethanol. cyclohex-2-en-1-ol, diphenylmethanol and p-methoxybenzyl alcohol by treatment with methanesulfonyl chloride and triethylamine in dichloro- or trichloro-methane at - 20 to 0 °C. The mesylates. characterised in solution by $^1$H and $^{13}$C NMR at -20 °C, were obtained in satisfactory purity (ca. 95%) in cold solutions but they decomposed by reaction with chloride, triethylamine or the parent alcohol. Rate constants for solvolyses in aqueous acetone and aqueous ethanol have been determined by a fast response conductimetric method. Product selectivities for solvolyses of pmethoxybenzyl mesylate in aqueous ethanol and methanol at 0 °C have been determined by HPLC. From additional new or Iiterature kinetic data for solvolyses of corresponding bromides. chlorides and p-nitrobenzoates (OPNB). Br/CI. OMs/Br and OMs/OPNB rate ratios were calculated; the results are consistent with electronic effects stabilising the carbocationic transition states and increasing OMs/Br rate ratios for these SN 1 solvolyses; none of the evidence supports a geminal electronic effect on Br/CI rate ratios (e.g. caused by stabilisation of the initial state in pmethoxybenzyl chloride). Steric effects on ester /halide rate ratios for solvolyses of tertiary substrates are confirmed. Relative rates over a 10$^{16}$ range for ester and halide leaving groups are evaluated for solvolyses of 1-phenylethyl substrates in 80% ethanol-water. updating previous work by Noyce et al. (1972)

Contrasting reservoirs for Schistosoma japonicum between marshland and hilly regions in Anhui, China--a two-year longitudinal parasitological survey.

Schistosoma japonicum remains highly endemic in many counties in China and has recently re-emerged, to a large extent, in previously controlled areas. To test the hypothesis that small rodents and less agriculturally important domestic animals such as dogs and cats may play an important role in the transmission and potential re-emergence of this disease, an annual investigation of S. japonicum among humans, domestic animals and rodents, combined with detailed surveys of the snail intermediate host, was performed across 3 marshland villages and 3 hilly villages in Anhui province of China over 2 consecutive years. The highest infection prevalence and intensity observed across all mammals was in rodents in the hilly region; while in the marshland, bovines were suspected as the main reservoirs. However, relatively high infection prevalence levels were also found in dogs and cats in both regions. Such results may have implications for the current human- and bovine-oriented control policy for this medically and veterinarily important disease, particularly within the hilly regions of mainland China

Simple model for tuberculosis in cattle and badgers

As an aid to the study of bovine tuberculosis (TB), a simple model has been developed of an epidemic involving two species, cattle and badgers. Each species may infect the other. The proportion of animals affected is assumed relatively small so that the usual nonlinear aspects of epidemic theory are avoided. The model is used to study the long-run and transient effect on cattle of culling badgers and the effect of a period without routine testing for TB, such as occurred during the 2001 epidemic of foot-and-mouth disease in Great Britain. Finally, by examining the changes in cattle TB over the last 15 years, and with some other working assumptions, it is estimated that the net reproduction number of the epidemic is 1.1. The implications for controlling the disease are discussed

Embryologically Based Classification Specifies Gender Differences in the Prevalence of Orofacial Cleft Subphenotypes

Background: A recently published validated classification system divides all orofacial cleft (OFC) subphenotypes into groups based on underlying developmental mechanisms, that is, fusion and differentiation, and their timing, that is, early and late periods, in embryogenesis of the primary and secondary palates. Aims: The aim of our study was to define gender differences in prevalence for all subphenotypes in newborns with OFC in the Netherlands. Methods: This was a retrospective cross-sectional study on children with OFC born from 2006 to 2016. Clefts were classified in early (E-), late (L-), and early/late (EL-) embryonic periods, in primary (P-), secondary (S-), and primary/secondary (PS-) palates, and further divided into fusion (F-), differentiation (D-), and fusion/differentiation (FD-) defects, respectively. Results: A total of 2089 OFC children were analyzed (1311 males and 778 females). Orofacial cleft subphenotypes in females occurred significantly more frequent in the L-period compared to males (66% vs 55%, P = .000), whereas clefts in males occurred significantly more in the EL-periods (40% vs 27%, P = .000). Females had significantly more S-palatal clefts (42% vs 23%, P = .000), while males had significantly more PS-palatal clefts (44% vs 30%, P = .000). Furthermore, the clefts in females were significantly more frequent the result of an F-defect (60% vs 52%, P = .000). Conclusions: Orofacial cleft in females mainly occur in the L-period are mostly S-palatal clefts, and are usually the result of an F-defect. Orofacial cleft in males more commonly occur in the EL-periods, are therefore more often combined PS-palatal clefts, and are more frequent D- and FD-defects

FiberGLAST: a scintillating fiber approach to the GLAST mission

FiberGLAST is a scintillating fiber gamma-ray detector designed for the GLAST mission. The system described below provides superior effective area and field of view for modest cost and risk. An overview of the FiberGLAST instrument is presented, as well as a more detailed description of the principle elements of the primary detector volume. The triggering and readout electronics are described, and Monte Carlo Simulations of the instrument performance are presented

Upturn observed in heavy nuclei to iron ratios by the ATIC-2 experiment

The ratios of fluxes of heavy nuclei from sulfur (Z=16) to chromium (Z=24) to the flux of iron were measured by the ATIC-2 experiment. The ratios are decreasing functions of energy from 5 GeV/n to approximately 80 GeV/n, as expected. However, an unexpected sharp upturn in the ratios are observed for energies above 100 GeV/n for all elements from Z=16 to Z=24. Similar upturn but with lower amplitude was also discovered in the ATIC-2 data for the ratio of fluxes of abundant even nuclei (C, O, Ne, Mg, Si) to the flux of iron. Therefore the spectrum of iron is significantly different from the spectra of other abundant even nuclei.Comment: 4 pages, LaTeX2e, a paper for 23rd European Cosmic Ray Symposium (2012

Geant4 Simulation of Air Showers using Thinning Method

No abstract availabl

Beam test results for the FiberGLAST instrument

The FiberGLAST scintillating fiber telescope is a large-area instrument concept for NASA\u27s GLAST program. The detector is designed for high-energy gamma-ray astronomy, and uses plastic scintillating fibers to combine a photon pair tracking telescope and a calorimeter into a single instrument. A small prototype detector has been tested with high energy photons at the Thomas Jefferson National Accelerator Facility. We report on the result of this beam test, including scintillating fiber performance, photon track reconstruction, angular resolution, and detector efficiency

Paleo-denudation rates suggest variations in runoff drove aggradation during last glacial cycle, Crete, Greece

Fluvial aggradation and incision are often linked to Quaternary climate cycles, but it usually remains unclear whether variations in runoff or sediment supply or both drive channel response to climate variability. Here we quantify sediment supply with paleo-denudation rates and provide geochronological constraints on aggradation and incision from the Sfakia and Elafonisi alluvial-fan sequences in Crete, Greece. We report seven optically stimulated luminescence and ten radiocarbon ages, eight 10Be and eight 36Cl denudation rates from modern channel and terrace sediments. For five samples, 10Be and 36Cl were measured on the same sample by measuring 10Be on chert and 36Cl on calcite. Results indicate relatively steady denudation rates throughout the past 80 kyr, but the aggradation and incision history indicates a link with climate shifts. At the Elafonisi fan, we identify four periods of aggradation coinciding with Marine Isotope Stages (MIS) 2, 4, 5a/b, and likely 6, and three periods of incision coinciding with MIS 1, 3, and likely 5e. At the Sfakia fan, rapid aggradation occurred during MIS 2 and 4, followed by incision during MIS 1. Nearby climate and vegetation records show that MIS 2, 4, and 6 stadials were characterized by cold and dry climates with sparse vegetation, whereas forest cover and more humid conditions prevailed during MIS 1, 3, and 5. Our data thus suggest that past changes in climate had little effect on landscape-wide denudation rates but exerted a strong control on the aggradation–incision behaviour of alluvial channels on Crete. During glacial stages, we attribute aggradation to hillslope sediment release promoted by reduced vegetation cover and decreased runoff; conversely, incision occurred during relatively warm and wet stages due to increased runoff. In this landscape, past hydroclimate variations outcompeted changes in sediment supply as the primary driver of alluvial deposition and incision