Cloning, purification and characterization of the 6-phospho-3-hexulose isomerase YckF from Bacillus subtilis

The enzyme 6-phospho-3-hexulose isomerase (YckF) from Bacillus subtilis has been prepared and crystallized in a form suitable for X-ray crystallographic analysis. Crystals were grown by the hanging-drop method at 291 K using polyethylene glycol 2000 monomethylether as precipitant. They diffract beyond 1.7 A using an in-house Cu Kalpha source and belong to either space group P6(5)22 or P6(1)22, with unit-cell parameters a = b = 72.4, c = 241.2 A, and have two molecules of YckF in the asymmetric unit

Tradition and rural modernity in Mary Webb’s Shropshire: Precious Bane in context

In Precious Bane (1924), Mary Webb explores the potential of traditional ways of seeing to enable the renaturing of landscapes depleted and increasingly denatured by normalized exploitative capitalist farming practices. Webb does not unquestioningly celebrate tradition, as is apparent from the ambivalent representation of Beguildy, or the cruelty of Huglet and Grimble. Nevertheless, the novel challenges the post-Enlightenment hierarchical opposition between a supposedly rational modernity, and the allegedly ignorant superstition of those whose lives are still structured around traditional ways of understanding the world. This distinction has often been central to the promotion of what Karl Bell calls the "mythification of the modern." Bell has in mind the uncritical assumption that all things modern are a source of progress, especially when, as is often the case, the modern is understood to mean a world dominated and structured by instrumentalism and laissez-faire capitalism. In Precious Bane, the provisional and "mythopoeic" qualities of both traditional beliefs and practices and different versions of rural modernity are explored through the fraught relationships between Prue Sarn, the first-person narrator; her atheist brother Gideon (who rejects tradition, and fully embraces modern laissez-faire capitalism); and the cunning-man Beguildy (who exemplifies tradition)

Dark-Ages Reionisation & Galaxy Formation Simulation XVI: The Thermal Memory of Reionisation

Intergalactic medium temperature is a powerful probe of the epoch of reionisation, as information is retained long after reionisation itself. However, mean temperatures are highly degenerate with the timing of reionisation, with the amount heat injected during the epoch, and with the subsequent cooling rates. We post-process a suite of semi-analytic galaxy formation models to characterise how different thermal statistics of the intergalactic medium can be used to constrain reionisation. Temperature is highly correlated with redshift of reionisation for a period of time after the gas is heated. However as the gas cools, thermal memory of reionisation is lost, and a power-law temperature-density relation is formed, $T = T_0(1+\delta)^{1-\gamma}$ with $\gamma \approx 1.5$. Constraining our model against observations of electron optical depth and temperature at mean density, we find that reionisation likely finished at $z_{\rm{reion}} = 6.8 ^{+ 0.5} _{-0.8}$ with a soft spectral slope of $\alpha = 2.8 ^{+ 1.2} _{-1.0}$. By restricting spectral slope to the range $[0.5,2.5]$ motivated by population II synthesis models, reionisation timing is further constrained to $z_{\rm{reion}} = 6.9 ^{+ 0.4} _{-0.5}$. We find that, in the future, the degeneracies between reionisation timing and background spectrum can be broken using the scatter in temperatures and integrated thermal history.Comment: 17 pages, 17 figures, Accepted for publication in MNRA

Competitive formation of spiro and ansa derivatives in the reactions of tetrafluorobutane-1,4-diol with hexachlorocyclotriphosphazene: a comparison with butane-1,4-diol

Reaction of hexachlorocyclotriphosphazene, N3P3Cl6 (1), in two stoichiometries (1:1.2 and 1:3) with the sodium derivative of the fluorinated diol, 2,2,3,3-tetrafluorobutane-1,4-diol, (2), in THF solution at room temperature afforded six products, whose structures have been characterized by X-ray crystallography and 1H, 19F and 31P NMR spectroscopy: the mono-spiro compound, N3P3Cl4(OCH2CF2CF2CH2O), (3), its ansa isomer, (4), a di-spiro derivative N3P3Cl2(OCH2CF2CF2CH2O)2, (5), its spiro-ansa (6) and non-gem cis bis-ansa (7) isomers and a tri-spiro compound N3P3(OCH2CF2CF2CH2O)3, (8). The tri-spiro derivative (8) was also formed in the reaction of the ansa compound (4) with diol (2) in a 1:3 ratio in THF at room temperature. The reactions of (1) with step-wise additions of (2) were also investigated at low temperature (-780C) to give the same range of products as at room temperature. The results of all reactions are compared with previous work on the reactions of (1) with butane-1,4-diol/pyridine mixtures and with the reaction of hexafluorocyclotriphosphazene, N3P3F6 (9), with the silyl derivative of the diol (2), (Me3SiOCH2CF2)2, in a 1:0.4 mole ratio in the same solvent, THF

Methane hydrate recycling offshore of Mauritania probably after the last glacial maximum

To what extent methane liberated from marine hydrate will enter the ocean during a warmer world is unknown. Although methane release due to hydrate dissociation has been modelled, it is unclear whether or not methane will reach the seafloor during a warmer world and therefore contribute to oceanic and atmospheric budgets. Here we show, using a new three-dimensional (3-D) seismic dataset, that some hydrate deposits surround the gas chimneys passing through the HSZ. Bottom water warming since the last glacial maximum (LGM) is interpreted to cause hydrate dissociation but critically some of the released methane was not vented to the ocean. The released gas caused seal failure and free gas entered the hydrate stability zone (HSZ) through vertical gas chimneys to where new hydrate accumulations formed. This process is a new evidence for methane recycling and could account in part for the lack of methane in ice core records that cover warming events during the late Quaternary. This research provides new insight into how methane could be recycled rather than vented during a warmer world

Identification of single-site gold catalysis in acetylene hydrochlorination

There remains considerable debate over the active form of gold under operating conditions of a recently validated gold catalyst for acetylene hydrochlorination. We have performed an in situ x-ray absorption fine structure study of gold/carbon (Au/C) catalysts under acetylene hydrochlorination reaction conditions and show that highly active catalysts comprise single-site cationic Au entities whose activity correlates with the ratio of Au(I):Au(III) present. We demonstrate that these Au/C catalysts are supported analogs of single-site homogeneous Au catalysts and propose a mechanism, supported by computational modeling, based on a redox couple of Au(I)-Au(III) species. View Full Tex

Stereoisomerism in pentaerythritol-bridged cyclotriphosphazene tri-spiranes: spiro and ansa 1,3-propanediyldioxy disubstituted derivatives

Four isomeric products were isolated and purified from the reaction of 1,3-propanediol with the tetra-spirane cyclophosphazene-organophosphate compound (1): viz. the di-monospiro (2a), di-monoansa (2b) and two monospiro-monoansa derivatives (2c) and (2d). It is shown by 31P NMR spectroscopy on addition of a chiral solvating agent (CSA) that both the di-monospiro (2a) and di-monoansa (2b) derivatives are racemates, as expected, whereas no splitting of NMR signals occurred on addition of CSA to solutions of (2c) and (2d). It is found by X-ray crystallography that the two monospiro-monoansa spirane derivatives, (2c) and (2d), are meso diastereoisomers, which represent a new case of the stereochemistry of bis di-substituted cyclophosphazene derivatives of (1). It is also observed from the 31P NMR spectrum of the reaction mixture, supported by the yields of pure compounds, that formation of a spiro group is about 4.5 times more likely than that of an ansa moiety under the conditions of the reaction

Majority Voting Approach to Ransomware Detection

Crypto-ransomware remains a significant threat to governments and companies alike, with high-profile cyber security incidents regularly making headlines. Many different detection systems have been proposed as solutions to the ever-changing dynamic landscape of ransomware detection. In the majority of cases, these described systems propose a method based on the result of a single test performed on either the executable code, the process under investigation, its behaviour, or its output. In a small subset of ransomware detection systems, the concept of a scorecard is employed where multiple tests are performed on various aspects of a process under investigation and their results are then analysed using machine learning. The purpose of this paper is to propose a new majority voting approach to ransomware detection by developing a method that uses a cumulative score derived from discrete tests based on calculations using algorithmic rather than heuristic techniques. The paper describes 23 candidate tests, as well as 9 Windows API tests which are validated to determine both their accuracy and viability for use within a ransomware detection system. Using a cumulative score calculation approach to ransomware detection has several benefits, such as the immunity to the occasional inaccuracy of individual tests when making its final classification. The system can also leverage multiple tests that can be both comprehensive and complimentary in an attempt to achieve a broader, deeper, and more robust analysis of the program under investigation. Additionally, the use of multiple collaborative tests also significantly hinders ransomware from masking or modifying its behaviour in an attempt to bypass detection.Comment: 17 page

Structural investigations of phosphorus-nitrogen compounds. 7. Relationships between physical properties, electron densities, reaction mechanisms and hydrogen-bonding motifs of N3P3Cl(6-n)(NHBut)(n) derivatives

A series of compounds of the N3P3Cl(6-n)(NHBut)n family (where n = 0, 1, 2, 4 and 6) are presented and their molecular parameters are related to trends in physical properties, which provides insight into a potential reaction mechanism for nucleophilic substitution. The crystal structures of N3P3Cl5(NHBut) and N3P3Cl2(NHBut)4 have been determined at 120K and those of N3P3Cl6 and N3P3Cl4(NHBut)2 have been re-determined at 120K. These are compared with the known structure of N3P3(NHBut)6 studied at 150K. Trends in molecular parameters (phosphazene ring, P-Cl & P-N(HBut) distances, PCl2 angles and endo- and exo-cyclic phosphazene ring parameters) across the series are observed. Hydrogen-bonding motifs are identified, characterised and compared. Both the molecular and hydrogen bonding parameters are related to the electron distribution in bonds and the derived basicities of the cyclophosphazene series of compounds. These findings provide evidence for a proposed mechanism for nucleophilic substitution at a phosphorus site bearing a PCl(NHBut) moiety