Chemistry by Mobile Phone (or how to justify more time at the bar)

By combining automatic environment monitoring with Java smartphones a system has been produced for the real-time monitoring of experiments whilst away from the lab. Changes in the laboratory environment are encapsulated as simple XML messages, which are published using an MQTT compliant broker. Clients subscribe to the MQTT stream, and produce a user display. An MQTT client written for the Java MIDP platform, can be run on a smartphone with a GPRS Internet connection, freeing us from the constraints of the lab. We present an overview of the technologies used, and how these are helping chemists make the best use of their time

Development of a low-maintenance measurement approach to continuously estimate methane emissions: a case study

The chemical breakdown of organic matter in landfills represents a significant source of methane gas (CH4). Current estimates suggest that landfills are responsible for between 3% and 19% of global anthropogenic emissions. The net CH4 emissions resulting from biogeochemical processes and their modulation by microbes in landfills are poorly constrained by imprecise knowledge of environmental constraints. The uncertainty in absolute CH4 emissions from landfills is therefore considerable. This study investigates a new method to estimate the temporal variability of CH4 emissions using meteorological and CH4 concentration measurements downwind of a landfill site in Suffolk, UK from July to September 2014, taking advantage of the statistics that such a measurement approach offers versus shorter-term, but more complex and instantaneously accurate, flux snapshots. Methane emissions were calculated from CH4 concentrations measured 700 m from the perimeter of the landfill with observed concentrations ranging from background to 46.4 ppm. Using an atmospheric dispersion model, we estimate a mean emission flux of 709 μg m−2 s−1 over this period, with a maximum value of 6.21 mg m−2 s−1, reflecting the wide natural variability in biogeochemical and other environmental controls on net site emission. The emissions calculated suggest that meteorological conditions have an influence on the magnitude of CH4 emissions. We also investigate the factors responsible for the large variability observed in the estimated CH4 emissions, and suggest that the largest component arises from uncertainty in the spatial distribution of CH4 emissions within the landfill area. The results determined using the low-maintenance approach discussed in this paper suggest that a network of cheaper, less precise CH4 sensors could be used to measure a continuous CH4 emission time series from a landfill site, something that is not practical using far-field approaches such as tracer release methods. Even though there are limitations to the approach described here, this easy, low-maintenance, low-cost method could be used by landfill operators to estimate time-averaged CH4 emissions and their impact downwind by simultaneously monitoring plume advection and CH4 concentrations

A Physiologically Based Model of Orexinergic Stabilization of Sleep and Wake

The orexinergic neurons of the lateral hypothalamus (Orx) are essential for regulating sleep-wake dynamics, and their loss causes narcolepsy, a disorder characterized by severe instability of sleep and wake states. However, the mechanisms through which Orx stabilize sleep and wake are not well understood. In this work, an explanation of the stabilizing effects of Orx is presented using a quantitative model of important physiological connections between Orx and the sleep-wake switch. In addition to Orx and the sleep-wake switch, which is composed of mutually inhibitory wake-active monoaminergic neurons in brainstem and hypothalamus (MA) and the sleep-active ventrolateral preoptic neurons of the hypothalamus (VLPO), the model also includes the circadian and homeostatic sleep drives. It is shown that Orx stabilizes prolonged waking episodes via its excitatory input to MA and by relaying a circadian input to MA, thus sustaining MA firing activity during the circadian day. During sleep, both Orx and MA are inhibited by the VLPO, and the subsequent reduction in Orx input to the MA indirectly stabilizes sustained sleep episodes. Simulating a loss of Orx, the model produces dynamics resembling narcolepsy, including frequent transitions between states, reduced waking arousal levels, and a normal daily amount of total sleep. The model predicts a change in sleep timing with differences in orexin levels, with higher orexin levels delaying the normal sleep episode, suggesting that individual differences in Orx signaling may contribute to chronotype. Dynamics resembling sleep inertia also emerge from the model as a gradual sleep-to-wake transition on a timescale that varies with that of Orx dynamics. The quantitative, physiologically based model developed in this work thus provides a new explanation of how Orx stabilizes prolonged episodes of sleep and wake, and makes a range of experimentally testable predictions, including a role for Orx in chronotype and sleep inertia

Nuclear spirals as feeding channels to the Supermassive Black Hole: the case of the galaxy NGC 6951

We report the discovery of gas streaming motions along nuclear spiral arms towards the LINER nucleus of the galaxy NGC 6951. The observations, obtained using the GMOS integral field spectrograph on the Gemini North telescope, yielded maps of the flux distributions and gas kinematics in the Halpha, [NII]6584 and [SII]6717,31 emission lines of the inner 7x5 arcsec^2 of the galaxy. This region includes a circumnuclear star-forming ring with radius 500pc, a nuclear spiral inside the ring and the LINER nucleus. The kinematics of the ionized gas is dominated by rotation, but subtraction of a kinematic model of a rotating exponential disk reveals deviations from circular rotation within the nuclear ring which can be attributed to (1) streaming motions along the nuclear spiral arms and (2) a bipolar outflow which seems to be associated to a nuclear jet. On the basis of the observed streaming velocities and geometry of the spiral arms we estimate a mass inflow rate of ionized gas of 3x10^(-4) Msun/yr, which is of the order of the accretion rate necessary to power the LINER nucleus of NGC 6951. Similar streaming motions towards the nucleus of another galaxy with LINER nucleus -- NGC 1097 -- have been reported by our group in a previous paper. Taken together, these results support a scenario in which nuclear spirals are channels through which matter is transferred from galactic scales to the nuclear region to feed the supermassive black hole.Comment: 25 pages, 6 eps figures, accepted for publication in Ap

Enantioselective isothiourea catalysed Michael-Michael-lactonisation cascade; synthesis of δ-lactones and 1,2,3,4-substituted cyclopentanes

The authors thank the EPSRC (ERTR – grant code EP/J500549/1; ABF - grant code EP/J018139/1), the Spanish government for a FPU Fellowship and the University of Seville (V Plan Propio de Investigación) for financial support (PER). This work was supported by the European Research Council under the European Union’s Seventh Framework Programme (FP7/2007–2013) ERC grant agreement no. 279850. ADS thanks the Royal Society for a Wolfson Research Merit Award.This manuscript describes the application of α,β-unsaturated acyl ammonium intermediates in a Michael-Michael-lactonisation cascade process to furnish δ-lactones. Generation of α,β-unsaturated acyl ammonium intermediates was achieved upon addition of isothiourea catalyst HyperBTM into α,β-unsaturated acid chlorides. Subsequent reaction with enonemalonates gave access to δ-lactones in 20-64% yield, 72.5:27.5 to 95:5 er and 81:19 to >95:5 dr. Additionally, application of a ring-opening protocol yielded1,2,3,4-substituted cyclopentanes in 28-77% yield, 76:24 to 98:2 er and 86:14 to >95:5 dr. Interestingly, highest er was observed at high reaction temperatures, with 70˚C proving optimal. This effect was investigated by conducting an Eyring analysis, which indicated that differential activation entropy rather than differential activation enthalpy is responsible for enantiodiscrimination in this process.PostprintPeer reviewe

A z=5.34 Galaxy Pair in the Hubble Deep Field

We present spectrograms of the faint V-drop (V(606) = 28.1, I(814) = 25.6) galaxy pair HDF3-951.1 and HDF3-951.2 obtained at the Keck II Telescope. Fernandez-Soto, Lanzetta, & Yahil (1998) derive a photometric redshift of z(ph) = 5.28 (+0.34,-0.41; 2 sigma) for these galaxies; our integrated spectrograms show a large and abrupt discontinuity near 7710 (+- 5) Angstroms. This break is almost certainly due to the Lyman alpha forest as its amplitude (1 - fnu(short) / fnu(long) > 0.87; 95% confidence limit) exceeds any discontinuities observed in stellar or galaxian rest-frame optical spectra. The resulting absorption-break redshift is z=5.34 (+- 0.01). Optical/near-IR photometry from the HDF yields an exceptionally red (V(606)-I(814)) color, consistent with this large break. A more accurate measure of the continuum depression blueward of Lyman alpha utilizing the imaging photometry yields D(A) = 0.88. The system as a whole is slightly brighter than L*(1500) relative to the z~3 Lyman break population and the total star formation rate inferred from the UV continuum is ~22 h(50)^-2 M(sun) yr^-1 (q(0) = 0.5) assuming the absence of dust extinction. The two individual galaxies are quite small (size scales < 1 h(50)^-1 kpc). Thus these galaxies superficially resemble the Pascarelle etal (1996) ``building blocks''; if they comprise a gravitationally bound system, the pair will likely merge in a time scale ~100 Myr.Comment: 18 pages, 4 figures; accepted to A

Streaming Motions Towards the Supermassive Black Hole in NGC 1097

We have used GMOS-IFU and high resolution HST-ACS observations to map, in unprecedented detail, the gas velocity field and structure within the 0.7 kpc circumnuclear ring of the SBb LINER/Seyfert 1 galaxy NGC 1097. We find clear evidence of radial streaming motions associated with spiral structures leading to the unresolved (<3.5 parsecs) nucleus, which we interpret as part of the fueling chain by which gas is transported to the nuclear starburst and supermassive black hole.Comment: 4 pages, 3 figures using emulateapj. Accepted for publication in Astrophysical Journal Letters. Download high-resolution version from http://www.astro.uu.se/~kambiz/DOC/paper-N1097.pd

A Bestiary of Higher Dimensional Taub-NUT-AdS Spacetimes

We present a menagerie of solutions to the vacuum Einstein equations in six, eight and ten dimensions. These solutions describe spacetimes which are either locally asymptotically adS or locally asymptotically flat, and which have non-trivial topology. We discuss the global structure of these solutions, and their relevance within the context of M-theory.Comment: 11 pages, LaTex(v4: Comments and references added