Kinetics of the ClO + CH3O2 reaction over the temperature range T = 250 – 298 K

The kinetics of the potentially atmospherically important ClO + CH3O2 reaction (1) have been studied over the range T = 250–298 K at p = 760 Torr using laser flash photolysis radical generation, coupled with time resolved ultraviolet absorption spectroscopy, employing broad spectral monitoring using a charge coupled device detector array. ClO radicals were monitored unequivocally using this technique, and introduction of CH3O2 precursors ensured known initial methylperoxy radical concentrations. ClO temporal profiles were thereafter analysed to extract kinetic parameters for reaction (1). A detailed sensitivity analysis was also performed to examine any potential systematic variability in k1 as a function of kinetic or physical uncertainties. The kinetic data recorded in this work show good agreement with the most recent previous study of this reaction, reported by Leather et al. The current work reports an Arrhenius parameterisation for k1, given by: k(1)(T) = 2.2+3.4-1.3 x 10^-11 e(-(642+-253)K/T)cm^3 molecule^-1 s^-1. This work therefore concurs with that of Leather et al. implying that the title reaction is potentially less significant in the atmosphere than inferred from preceding studies. However, reaction (1) is evidently a non-terminating radical reaction, whose effects upon atmospheric composition therefore need to be ascertained through atmospheric model studies

Kinetics of the ClO + HOreaction over the temperature range T = 210–298 K

The rate coefficient for the atmospherically important radical reaction: ClO + HO2 → Productswhich leads to ozone depletion, has been studied over the temperature range T = 210–298 K and at ambient pressure p = 760 ± 20 Torr. The reaction was studied using laser flash photolysis radical generation coupled with broadband charge coupled device absorption spectroscopy employing a two-dimensional charge-coupled-device (CCD) detection system. ClO radicals were generated following the photolysis of Cl2 and Cl2O gas mixtures diluted in nitrogen and oxygen. ClO radicals were monitored using broadband fingerprinting of their characteristic vibronic (A2Π ← X2Π) spectral structure, representing a definitive monitoring of this radical. Addition of hydroperoxy radical precursors to the gas mixture (methanol and oxygen) subsequently led to a competition for photolytically generated Cl atoms and a simultaneous prompt formation of both ClO and HO2 radicals. Detailed analysis and modelling of the radical production routes provided a degree of constraint into numerical integration simulations which were then used to interrogate and fit to ClO temporal profiles to extract the rate coefficient k1. The ambient temperature (T = 298 K) rate coefficient reported is k1 = (8.5 ± 1.5) × 10−12 cm3 molecule−1 s−1. The rate coefficient, k1, is described by the Arrhenius expression:where errors are 1σ statistical only. This significant rate coefficient is greater than previously reported, with a stronger negative temperature dependence than previously observed. Consequently this suggests that the contribution of reaction (1) to ozone loss, in particular at mid-latitudes might be currently underestimated in models. This work reports atmospheric pressure kinetic parameters for this reaction which are greater than those reported from low pressure studies, perhaps supporting ClO and HO2 association as predicted by previous theoretical studies of this process and highlighting the need for further pressure dependent experimental studies of the title reaction, which has been demonstrated here to be effective as an ozone loss process over a wide temperature range

Pleistocene uplift and palaeoenvironments of Macquarie Island: evidence from palaeobeaches and sedimentary deposits

Macquarie Island (54°30'S, 159°00'E) is an emergent part of the Macquarie Ridge Complex composed of ocean-floor rocks of Miocene age now 4000 m above the ocean floor. A number of landforms, including palaeobeaches now above sea level (a.s.l.)on Macquarie Island, were formed by marine erosion during uplift of the island. During the last Pleistocene period of low sea level (c. 20 ka) the island was three times larger than now. Thermoluminescence (TL) dating of two palaeobeaches indicates Pleistocene ages: 172 ± 40 ka for one at 100 m a.s.l. and 340 ± 80 ka for another at 263 m a.s.l. Matching the altitude sequence of palaeobeaches on Macquarie Island with the pattern of peaks in world sea level determined from deep sea cores allows an independent estimate of beach ages. Comparison of the altitude and sea level sequences most plausibly places the 100 m palaeobeach in Oxygen Isotope Stage 5e (130-125 ka) and the 263 m palaeobeach in Stage 9 (340-330 ka), matching reasonably with the TL dates. Other palaeobeaches at about 50 m and 170-190 m a.s.l. then correlate with high sea levels. We calculate an average rate of uplift forthe island of 0.8 mma-I . At this rate, 4000 m of Macquarie Ridge uplift would have taken about five million years and the top of the island may first have emerged some 700 to 600 ka. During the six Pleistocene glacial-interglacial cycles since then, there has been periglacial rather than glacial activity on cold uplands, but conditions suitable for vegetation of the present type persisted close to sea level

Improving Fab’ fragment retention in an autonucleolytic Escherichia coli strain by swapping periplasmic nuclease translocation signal from OmpA to DsbA

OBJECTIVES: To reduce unwanted Fab’ leakage from an autonucleolytic Escherichia coli strain, which co-expresses OmpA-signalled Staphylococcal nuclease and Fab’ fragment in the periplasm, by substituting in Serratial nuclease and the DsbA periplasm translocation signal as alternatives. RESULTS: We attempted to genetically fuse a nuclease from Serratia marcescens to the OmpA signal peptide but plasmid construction failed, possibly due to toxicity of the resultant nuclease. Combining Serratial nuclease to the DsbA signal peptide was successful. The strain co-expressing this nuclease and periplasmic Fab’ grew in complex media and exhibited nuclease activity detectable by DNAse agar plate but its growth in defined medium was retarded. Fab’ coexpression with Staphylococcal nuclease fused to the DsbA signal peptide resulted in cells exhibiting nuclease activity and growth in defined medium. In cultivation to high cell density in a 5 l bioreactor, DsbA-fused Staphylococcal nuclease co-expression coincided with reduced Fab’ leakage relative to the original autonucleolytic Fab’ strain with OmpA-fused staphylococcal nuclease. CONCLUSIONS: We successfully rescued Fab’ leakage back to acceptable levels and established a basis for future investigation of the linkage between periplasmic nuclease expression and leakage of co-expressed periplasmic Fab’ fragment to the surrounding growth media

The sensitivity and specificity of a diagnostic test of sequence-space synesthesia

People with sequence-space synaesthesia (SSS) report stable visuo-spatial forms corresponding to numbers, days and months (amongst others). This type of synaesthesia has intrigued scientists for over 130 years but the lack of an agreed upon tool for assessing it has held back research on this phenomenon. The present study builds on previous tests by measuring the consistency of spatial locations that is known to discriminate controls from synaesthetes. We document, for the first time, the sensitivity and specificity of such a test and suggest a diagnostic cut-off point for discriminating between the groups based on the area bounded by different placement attempts with the same item

The hand of Homo naledi

A nearly complete right hand of an adult hominin was recovered from the Rising Star cave system, South Africa. Based on associated hominin material, the bones of this hand are attributed to Homo naledi. This hand reveals a long, robust thumb and derived wrist morphology that is shared with Neandertals and modern humans, and considered adaptive for intensified manual manipulation. However, the finger bones are longer and more curved than in most australopiths, indicating frequent use of the hand during life for strong grasping during locomotor climbing and suspension. These markedly curved digits in combination with an otherwise human-like wrist and palm indicate a significant degree of climbing, despite the derived nature of many aspects of the hand and other regions of the postcranial skeleton in H. naledi

Fungal iron availability during deep seated candidiasis is defined by a complex interplay involving systemic and local events

Peer reviewedPublisher PD

The molecular dimension of microbial species: 1. Ecological distinctions among, and homogeneity within, putative ecotypes of Synechococcus inhabiting the cyanobacterial mat of Mushroom Spring, Yellowstone National Park

© 2015 Becraft, Wood, Rusch, Kühl, Jensen, Bryant, Roberts, Cohan and Ward. Based on the Stable Ecotype Model, evolution leads to the divergence of ecologically distinct populations (e.g., with different niches and/or behaviors) of ecologically interchangeable membership. In this study, pyrosequencing was used to provide deep sequence coverage of Synechococcus psaA genes and transcripts over a large number of habitat types in the Mushroom Spring microbial mat. Putative ecological species (putative ecotypes), which were predicted by an evolutionary simulation based on the Stable Ecotype Model (Ecotype Simulation), exhibited distinct distributions relative to temperature-defined positions in the effluent channel and vertical position in the upper 1 mm-thick mat layer. Importantly, in most cases variants predicted to belong to the same putative ecotype formed unique clusters relative to temperature and depth in the mat in canonical correspondence analysis, supporting the hypothesis that while the putative ecotypes are ecologically distinct, the members of each ecotype are ecologically homogeneous. Putative ecotypes responded differently to experimental perturbations of temperature and light, but the genetic variation within each putative ecotype was maintained as the relative abundances of putative ecotypes changed, further indicating that each population responded as a set of ecologically interchangeable individuals. Compared to putative ecotypes that predominate deeper within the mat photic zone, the timing of transcript abundances for selected genes differed for putative ecotypes that predominate in microenvironments closer to upper surface of the mat with spatiotemporal differences in light and O2 concentration. All of these findings are consistent with the hypotheses that Synechococcus species in hot spring mats are sets of ecologically interchangeable individuals that are differently adapted, that these adaptations control their distributions, and that the resulting distributions constrain the activities of the species in space and time

Dimensionality and dynamics in the behavior of C. elegans

A major challenge in analyzing animal behavior is to discover some underlying simplicity in complex motor actions. Here we show that the space of shapes adopted by the nematode C. elegans is surprisingly low dimensional, with just four dimensions accounting for 95% of the shape variance, and we partially reconstruct "equations of motion" for the dynamics in this space. These dynamics have multiple attractors, and we find that the worm visits these in a rapid and almost completely deterministic response to weak thermal stimuli. Stimulus-dependent correlations among the different modes suggest that one can generate more reliable behaviors by synchronizing stimuli to the state of the worm in shape space. We confirm this prediction, effectively "steering" the worm in real time.Comment: 9 pages, 6 figures, minor correction