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Measuring multiple 17O–13C J-couplings in naphthalaldehydic acid: a combined solid state NMR and density functional theory approach
A combined multinuclear solid state NMR and gauge included projected augmented wave, density functional theory (GIPAW DFT) computational approach is evaluated to determine the four heteronuclear 1J(13C,17O) couplings in solid 17O enriched naphthalaldehydic acid. Direct multi-field 17O magic angle spinning (MAS), triple quantum MAS (3QMAS) and double rotation (DOR) experiments are initially utilised to evaluate the accuracy of the DFT approximations used in the calculation of the isotropic chemical shifts (diso), quadrupole coupling constants (CQ) and asymmetry (ZQ) parameters. These combined approaches give diso values of 313, 200 and 66 ppm for the carbonyl (CQO), ether (–O–) and hydroxyl (–OH) environments, respectively, with the corresponding measured quadrupole products (PQ) being 8.2, 9.0 and 10.6 MHz. The geometry optimised DFT structure derived using the CASTEP code gives firm agreement with the shifts observed for the ether (diso = 223, PQ = 9.4 MHz) and hydroxyl (diso = 62, PQ = 10.5 MHz) environments but the unoptimised experimental XRD structure has better agreement for the carbonyl group (diso = 320, PQ = 8.3 MHz). The determined diso and ZQ values are shown to be consistent with bond lengths closer to 1.222 Å (experimental length) rather than the geometry optimised length of 1.238 Å. The geometry optimised DFT 1J(13C,17O) coupling to the hydroxyl is calculated as 20 Hz and the couplings to the ether were calculated to be 37 (O–CQO) and 32 (O–C–OH) Hz. The scalar coupling parameters for the unoptimised experimental carbonyl group predict a 1J(13C,17O) value of 28 Hz, whilst optimisation gives a value of 27 Hz. These calculated 1J(13C,17O) couplings, together with estimations of the probability of each O environment being isotopically labelled (determined by electrospray ionisation mass spectrometry) and the measured refocussable transverse dephasing (T2 0) behaviour, are combined to simulate the experimental decay behaviour. Good agreement between the measured and calculated decay behaviour is observed
Increased uptake and improved outcomes of bowel cancer screening with a faecal immunochemical test: results from a pilot study within the national screening programme in England
The funding for the evaluation of the pilot was provided by the National Office of the NHS Cancer Screening Programmes (now part of Public Health England)
Thunderclap headache triggered by micturition: responsive to nimodipine
Primary thunderclap headache (TCH) is a rare condition, of which the onset can be triggered by coughing, exercise, and sexual activity. Micturition is a recognized trigger of secondary TCH with pheochromocytoma in bladder, but not of primary TCH. We describe a patient with an apparent primary TCH, which repeatedly occurred immediately after micturition until she achieved a therapeutic dosage of nimodipine
Ultra-Sensitive Hot-Electron Nanobolometers for Terahertz Astrophysics
The background-limited spectral imaging of the early Universe requires
spaceborne terahertz (THz) detectors with the sensitivity 2-3 orders of
magnitude better than that of the state-of-the-art bolometers. To realize this
sensitivity without sacrificing operating speed, novel detector designs should
combine an ultrasmall heat capacity of a sensor with its unique thermal
isolation. Quantum effects in thermal transport at nanoscale put strong
limitations on the further improvement of traditional membrane-supported
bolometers. Here we demonstrate an innovative approach by developing
superconducting hot-electron nanobolometers in which the electrons are cooled
only due to a weak electron-phonon interaction. At T<0.1K, the electron-phonon
thermal conductance in these nanodevices becomes less than one percent of the
quantum of thermal conductance. The hot-electron nanobolometers, sufficiently
sensitive for registering single THz photons, are very promising for
submillimeter astronomy and other applications based on quantum calorimetry and
photon counting.Comment: 19 pages, 3 color figure
The "Ram Effect": A "Non-Classical" Mechanism for Inducing LH Surges in Sheep
During spring sheep do not normally ovulate but exposure to a ram can induce ovulation. In some ewes an LH surge is induced immediately after exposure to a ram thus raising questions about the control of this precocious LH surge. Our first aim was to determine the plasma concentrations of oestradiol (E2) E2 in anoestrous ewes before and after the "ram effect" in ewes that had a "precocious" LH surge (starting within 6 hours), a "normal" surge (between 6 and 28h) and "late» surge (not detected by 56h). In another experiment we tested if a small increase in circulating E2 could induce an LH surge in anoestrus ewes. The concentration of E2 significantly was not different at the time of ram introduction among ewes with the three types of LH surge. "Precocious" LH surges were not preceded by a large increase in E2 unlike "normal" surges and small elevations of circulating E2 alone were unable to induce LH surges. These results show that the "precocious" LH surge was not the result of E2 positive feedback. Our second aim was to test if noradrenaline (NA) is involved in the LH response to the "ram effect". Using double labelling for Fos and tyrosine hydroxylase (TH) we showed that exposure of anoestrous ewes to a ram induced a higher density of cells positive for both in the A1 nucleus and the Locus Coeruleus complex compared to unstimulated controls. Finally, the administration by retrodialysis into the preoptic area, of NA increased the proportion of ewes with an LH response to ram odor whereas treatment with the α1 antagonist Prazosin decreased the LH pulse frequency and amplitude induced by a sexually active ram. Collectively these results suggest that in anoestrous ewes NA is involved in ram-induced LH secretion as observed in other induced ovulators
Integrating evolution into ecological modelling: accommodating phenotypic changes in agent based models.
PMCID: PMC3733718This is an open-access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.Evolutionary change is a characteristic of living organisms and forms one of the ways in which species adapt to changed conditions. However, most ecological models do not incorporate this ubiquitous phenomenon. We have developed a model that takes a 'phenotypic gambit' approach and focuses on changes in the frequency of phenotypes (which differ in timing of breeding and fecundity) within a population, using, as an example, seasonal breeding. Fitness per phenotype calculated as the individual's contribution to population growth on an annual basis coincide with the population dynamics per phenotype. Simplified model variants were explored to examine whether the complexity included in the model is justified. Outputs from the spatially implicit model underestimated the number of individuals across all phenotypes. When no phenotype transitions are included (i.e. offspring always inherit their parent's phenotype) numbers of all individuals are always underestimated. We conclude that by using a phenotypic gambit approach evolutionary dynamics can be incorporated into individual based models, and that all that is required is an understanding of the probability of offspring inheriting the parental phenotype
Properties of CO clathrate hydrates formed in the presence of MgSO solutions with implications for icy moons
There is evidence to suggest that clathrate hydrates have a significant effect on the surface geology of icy bodies in the Solar System. However the aqueous environments believed to be present on these bodies are likely to be saline rather than pure water. Laboratory work to underpin the properties of clathrates in such environments is lacking. We fill this gap by carrying out a laboratory investigation of the physical properties of CO clathrates produced in weak aqueous solutions of MgSO. We use synchrotron X-ray powder diffraction to investigate clathrates formed at high CO pressure in ice that has formed from aqueous solutions of MgSO. We measure the thermal expansion, density and dissociation properties of the clathrates under temperature conditions similar to those on icy Solar System bodies. We find that the sulphate solution inhibits the formation of clathrates by lowering their dissociation temperatures. Hysteresis is found in the thermal expansion coefficients as clathrates are cooled and heated; we attribute this to the presence of the salt in solution. The density derived from X-ray powder diffraction is temperature and pressure dependent. When comparing the density of CO clathrates to that of the solution in which they formed, we conclude that they sink in the oceans in which they form. We also find that the polymorph of ice present at low temperatures is Ih rather than Ic, which we attribute to the presence of the MgSO. We 1) conclude that the clathrate density has implications for their behaviour in satellite oceans as their sinking and floating capabilities are temperature and pressure dependent, 2) conclude that the presence of MgSO inhibits the formation of clathrates and in some cases may even affect their structure and 3) report the dominance of Ih throughout the experimental procedure despite Ic being the stable phase at low temperature
Utilisation of sexual health services by female sex workers in Nepal
Background
The Nepal Demographic Health Survey (NDHS) in 2006 showed that more than half (56%) of the women with sexually transmitted infections (STIs), including HIV, in Nepal sought sexual health services. There is no such data for female sex workers (FSWs) and the limited studies on this group suggest they do not even use routine health services. This study explores FSWs use of sexual health services and the factors associated with their use and non-use of services.
Methods
This study aimed to explore the factors associated with utilisation of sexual health services by FSWs in the Kathmandu Valley of Nepal, and it used a mixed-method
approach consisting of an interviewer administered questionnaire-based survey and in-depth interviews.
Results
The questionnaire survey, completed with 425 FSWs, showed that 90% FSWs self-reported sickness, and (30.8%) reported symptoms of STIs. A quarter (25%) of those reporting STIs had never visited any health facilities especially for sexual health services preferring to use non-governmental clinics (72%), private clinics (50%), hospital (27%)
and health centres (13%). Multiple regression analysis showed that separated, married and street- based FSWs were more likely to seek health services from the clinics or
hospitals. In- depth interviews with 15 FSWs revealed that FSWs perceived that personal, structural and socio-cultural barriers, such as inappropriate clinic opening hours,
discrimination, the judgemental attitude of the service providers, lack of confidentiality, fear of public exposure, and higher fees for the services as barriers to their access and utilisation of sexual health services.
Conclusion
FSWs have limited access to information and to health services, and operate under personal, structural and socio-cultural constraints. The ‘education’ to change individual behaviour, health worker and community perceptions, as well as the training of the health workers, is necessary
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