Ion-molecule reactions of O,S-Dimethyl methylphosphonothioate : Evidence for intramolecular sulfur oxidation during VX perhydrolysis

The alkaline perhydrolysis of the nerve agent O-ethyl S-[2-(diisopropylamino)ethyl] methylphosphonothioate (VX) was investigated by studying the ion-molecule reactions of HOO(-) with O,S-dimethyl methylphosphonothioate in a modified linear ion-trap mass spectrometer. In addition to simple proton transfer, two other abundant product ions are observed at m/z 125 and 109 corresponding to the S-methyl methylphosphonothioate and methyl methylphosphonate anions, respectively. The structure of these product ions is demonstrated by a combination of collision-induced dissociation and isotope-labeling experiments that also provide evidence for their formation by nucleophilic reaction pathways, namely, (i) S(N)2 at carbon to yield the S-methyl methylphosphonothioate anion and (ii) nucleophilic addition at phosphorus affording a reactive pentavalent intermediate that readily undergoes internal sulfur oxidation and concomitant elimination of CH(3)SOH to yield the methyl methylphosphonate anion. Consistent with previous Solution phase observations of VX perhydrolysis, the toxic P-O cleavage product is not observed in this VX model system and theoretical calculations identify P-O cleavage to be energetically uncompetitive. Conversely, intramolecular sulfur oxidation is calculated to be extremely exothermic and kinetically accessible explaining its competitiveness with the facile gas phase proton transfer process. Elimination of a sulfur moiety deactivates the nerve agent VX and thus the intramolecular sulfur oxidation process reported here is also able to explain the selective perhydrolysis of the nerve agent to relatively nontoxic products.

18.7”AX/VX型钢圈取放器——一种ROV携带的水下作业工具

目前,ROV(无人遥控潜水器)在水下工程和海洋石油工业上得到了广泛应用。ROV是通过各种水下作业工具来完成相应的作业任务。本文介绍了一种ROV携带海上石油钻井平台需要的新型水下作业工具一钢圈取放器。

Tumor hepático experimental (VX-2) em coelho: implantação do modelo no Brasil

Os estudos para a investigação de novas modalidades terapêuticas em biologia tumoral, deveriam passar por estudos experimentais prévios. Neste sentido dispõem-se hoje de uma grande variedade de modelos tumorais experimentais; em determinadas investigações faz-se necessária a adequação do modelo tumoral às necessidades biológicas, patológicas e experimentais dos estudos. Desta forma, em nosso serviço, buscávamos um modelo tumoral hepático para estudos experimentais que se adequasse às seguintes características: fácil manipulação, crescimento controlável, evolução e agressividade semelhantes aos seres humanos. Os dados da literatura nos levaram a busca do tumor hepático VX-2, em coelhos. Neste artigo discutimos as vantagens da utilização deste modelo experimental e a sua introdução em nosso país.

The fragmentation pathways of protonated Amiton in the gas phase : towards the structural characterisation of organophosphorus chemical warfare agents by electrospray ionisation tandem mass spectrometry

Amiton (O,O-diethyl-S-[2-(diethylamino)ethyl]phosphorothiolate), otherwise known as VG, is listed in schedule 2 of the Chemical Weapons Convention (CWC) and has a structure closely related to VX (O-ethyl-S-(2-diisopropylamino)ethylmethylphosphonothiolate). Fragmentation of protonated VG in the gas phase was performed using electrospray ionisation ion trap mass spectrometry (ESI-ITMS) and revealed several characteristic product ions. Quantum chemical calculations provide the most probable structures for these ions as well as the likely unimolecular mechanisms by which they are formed. The decomposition pathways predicted by computation are consistent with deuterium-labeling studies. The combination of experimental and theoretical data suggests that the fragmentation pathways of VG and analogous organophosphorus nerve agents, such as VX and Russian VX, are predictable and thus ESI tandem mass spectrometry is a powerful tool for the verification of unknown compounds listed in the CWC. Copyright (c) 2006 Commonwealth of Australia. Published by John Wiley & Sons, Ltd.

Reactions of the hydroperoxide anion with dimethyl methylphosphonate in an ion trap mass spectrometer : evidence for a gas phase alpha-effect

The gas phase degradation reactions of the chemical warfare agent (CWA) simulant, dimethyl methylphosphonate (DMMP), with the hydroperoxide anion (HOO(-)) were investigated using a modified quadrupole ion trap mass spectrometer. The HOO(-) anion reacts readily with neutral DMMP forming two significant product ions at m/z 109 and m/z 123. The major reaction pathways correspond to (i) the nucleophilic substitution at carbon to form \[CH(3)P(O)(OCH(3))O](-) (m/z 109) in a highly exothermic process and (ii) exothermic proton transfer. The branching ratios of the two reaction pathways, 89% and 11% respectively, indicate that the former reaction is significantly faster than the latter. This is in contrast to the trend for the methoxide anion with DMMP, where proton transfer dominates. The difference in the observed reactivities of the HOO(-) and CH(3)O(-) anions can be considered as evidence for an a-effect in the gas phase and is supported by electronic structure calculations at the B3LYP/aug-cc-pVTZ//B3LYP/6-31+G(d) level of theory that indicate the S(N)2(carbon) process has an activation energy 7.8 kJ mol(-1) lower for HOO(-) as compared to CH(3)O(-). A similar alpha-effect was calculated for nucleophilic addition-elimination at phosphorus, but this process an important step in the perhydrolysis degradation of CWAs in solution - was not observed to occur with DMMP in the gas phase. A theoretical investigation revealed that all processes are energetically accessible with negative activation energies. However, comparison of the relative Arrhenius pre-exponential factors indicate that substitution at phosphorus is not kinetically competitive with respect to the S(N)2(carbon) and deprotonation processes.

Defective in Cuticular Ridges (DCR) of Arabidopsis thaliana, a Gene Associated with Surface Cutin Formation, Encodes a Soluble Diacylglycerol Acyltransferase

A key step in the triacylglycerol (TAG) biosynthetic pathway is the final acylation of diacylglycerol (DAG) by DAG acyltransferase. In silico analysis has revealed that the DCR (defective in cuticular ridges) (At5g23940) gene has a typical HX4D acyltransferase motif at the N-terminal end and a lipid binding motif VX(2)GF at the middle of the sequence. To understand the biochemical function, the gene was overexpressed in Escherichia coli, and the purified recombinant protein was found to acylate DAG specifically in an acyl-CoA-dependent manner. Overexpression of At5g23940 in a Saccharomyces cerevisiae quadruple mutant deficient in DAG acyltransferases resulted in TAG accumulation. At5g23940 rescued the growth of this quadruple mutant in the oleate-containing medium, whereas empty vector control did not. Lipid particles were localized in the cytosol of At5g23940-transformed quadruple mutant cells, as observed by oil red O staining. There was an incorporation of 16-hydroxyhexadecanoic acid into TAG in At5g23940-transformed cells of quadruple mutant. Here we report a soluble acyl-CoA-dependent DAG acyltransferase from Arabidopsis thaliana. Taken together, these data suggest that a broad specific DAG acyltransferase may be involved in the cutin as well as in the TAG biosynthesis by supplying hydroxy fatty acid.

微动勘查方法在煤矿采区勘探中的应用研究

The conventional microtremor survey is based on the single point of exploration, which includes collecting field data，estimating the phase velocity, investing the dispersion curve and obtaining the S–wave velocity structure. In the case of large-scale exploration, and when making the two-dimensional velocity section, the inversion is quite time-consuming, laborious and its precision depends on the subjective interpretation, which makes the results differently from person to person. In fact，we do not need the S-wave velocity values but only need the relative variation of velocity. For these reasons, this paper is desired to calculate the apparent S-wave velocity (Vx) to replace the S-wave velocity inversion and to obtain the relative variation of the S-wave velocity. Using this method, we can decrease the analysts’ effect, shorten the data processing time and improve work efficiency. The apparent S-wave velocity is a variable of the surface wave property, which can clearly reflect the downcast columns, mined-out areas and other unusual geological bodies. In this paper, Matlab is used to establish the three-dimensional data volume of the apparent S-wave velocity, from which we can get any apparent S-wave velocity section we need. Through the application case, the designed method is proved to be reliable and effective. The downcast columns, mined-out areas and other unusual geological bodies can be clearly showed in the apparent S-wave velocity section. And from the contour of the apparent S-wave velocity, the interface shape of the major target layers can be controlled basically.

Self-organized vegetation patterning as a fingerprint of climate and human impact on semi-arid ecosystems

Spatially periodic vegetation patterns are well known in arid and semi-arid regions around the world. Mathematical models have been developed that attribute this phenomenon to a symmetry-breaking instability. Such models are based on the interplay between competitive and facilitative influences that the vegetation exerts on its own dynamics when it is constrained by arid conditions, but evidence for these predictions is still lacking. Moreover, not all models can account for the development of regularly spaced spots of bare ground in the absence of a soil prepattern. We applied Fourier analysis to high-resolution, remotely sensed data taken at either end of a 40-year interval in southern Niger. Statistical comparisons based on this textural characterization gave us broad-scale evidence that the decrease in rainfall over recent decades in the sub-Saharan Sahel has been accompanied by a detectable shift from homogeneous vegetation cover to spotted patterns marked by a spatial frequency of about 20 cycles km-1. Wood cutting and grazing by domestic animals have led to a much more marked transition in unprotected areas than in a protected reserve. Field measurements demonstrated that the dominant spatial frequency was endogenous rather than reflecting the spatial variation of any pre-existing heterogeneity in soil properties. All these results support the use of models that can account for periodic vegetation patterns without invoking substrate heterogeneity or anisotropy, and provide new elements for further developments, refinements and tests. This study underlines the potential of studying vegetation pattern properties for monitoring climatic and human impacts on the extensive fragile areas bordering hot deserts. Explicit consideration of vegetation self-patterning may also improve our understanding of vegetation and climate interactions in arid areas. © 2006 The Authors.

Gauge/gravity duality and the interplay of various fractional branes

We consider different types of fractional branes on a Z2 orbifold of the conifold and analyze in detail the corresponding gauge/gravity duality. The gauge theory possesses a rich and varied dynamics, both in the UV and in the IR. We find the dual supergravity solution, which contains both untwisted and twisted 3-form fluxes, related to what are known as deformation and N=2 fractional branes, respectively. We analyze the resulting renormalization group flow from the supergravity perspective, by developing an algorithm to easily extract it. We find hints of a generalization of the familiar cascade of Seiberg dualities due to a nontrivial interplay between the different types of fractional branes. We finally consider the IR behavior in several limits, where the dominant effective dynamics is either confining in a Coulomb phase or runaway, and discuss the resolution of singularities in the dual geometric background. © 2008 The American Physical Society.

Monopoles for gravitation and for higher spin fields

We consider massless higher spin gauge theories with both electric and magnetic sources, with a special emphasis on the spin two case. We write the equations of motion at the linear level (with conserved external sources) and introduce Dirac strings so as to derive the equations from a variational principle. We then derive a quantization condition that generalizes the familiar Dirac quantization condition, and which involves the conserved charges associated with the asymptotic symmetries for higher spins. Next we discuss briefly how the result extends to the nonlinear theory. This is done in the context of gravitation, where the Taub-NUT solution provides the exact solution of the field equations with both types of sources. We rederive, in analogy with electromagnetism, the quantization condition from the quantization of the angular momentum. We also observe that the Taub-NUT metric is asymptotically flat at spatial infinity in the sense of Regge and Teitelboim (including their parity conditions). It follows, in particular, that one can consistently consider in the variational principle configurations with different electric and magnetic masses. © 2006 The American Physical Society.

Lovelock terms and BRST cohomology

Lovelock terms are polynomial scalar densities in the Riemann curvature tensor that have the remarkable property that their Euler-Lagrange derivatives contain derivatives of the metric of an order not higher than 2 (while generic polynomial scalar densities lead to Euler-Lagrange derivatives with derivatives of the metric of order 4). A characteristic feature of Lovelock terms is that their first nonvanishing term in the expansion g λμ = η λμ + h λμ of the metric around flat space is a total derivative. In this paper, we investigate generalized Lovelock terms defined as polynomial scalar densities in the Riemann curvature tensor and its covariant derivatives (of arbitrarily high but finite order) such that their first nonvanishing term in the expansion of the metric around flat space is a total derivative. This is done by reformulating the problem as a BRST cohomological one and by using cohomological tools. We determine all the generalized Lovelock terms. We find, in fact, that the class of nontrivial generalized Lovelock terms contains only the usual ones. Allowing covariant derivatives of the Riemann tensor does not lead to a new structure. Our work provides a novel algebraic understanding of the Lovelock terms in the context of BRST cohomology. © 2005 IOP Publishing Ltd.

A note on spin-s duality

Duality is investigated for higher spin (s ≥ 2), free, massless, bosonic gauge fields. We show how the dual formulations can be derived from a common "parent", first-order action. This goes beyond most of the previous treatments where higher-spin duality was investigated at the level of the equations of motion only. In D = 4 spacetime dimensions, the dual theories turn out to be described by the same Pauli-Fierz (s = 2) or Fronsdal (s ≥ 3) action (as it is the case for spin 1). In the particular s = 2 D = 5 case, the Pauli-Fierz action and the Curtright action are shown to be related through duality. A crucial ingredient of the analysis is given by the first-order, gauge-like, reformulation of higher spin theories due to Vasiliev. © SISSA/ISAS 2003.

On stable non supersymmetric vacua at the bottom of cascading theories

We consider a wide class of cascading gauge theories which usually lead to runaway behaviour in the IR, and discuss possible deformations of the superpotential at the bottom of the cascade which stabilize the runaway direction and provide stable non-supersymmetric vacua. The models we find may allow for a weakly coupled supergravity analysis of dynamical supersymmetric breaking in the context of the gauge/string correspondence. © SISSA 2006.

Repeated concanavalin A challenge in mice induces an interleukin 10-producing phenotype and liver fibrosis.

Weekly injections of Concanavalin A (Con A) were performed in BALB/c mice to evaluate the pattern of cytokine production and liver injury. High serum levels of tumor necrosis factor alpha (TNF-alpha), interleukin 2 (IL-2), IL-4, and interferon gamma (IFN-gamma) were found in the serum after the first 2 injections of Con A but rapidly decreased from the third injection. Conversely, IL-10 serum levels after repeated Con A challenge increased by 7 times from week 1 to 20. In vivo depletion studies indicated that CD4(+) T cells are essential in IL-10 production. Hepatocyte necrosis was only observed after the first injections of Con A whereas centrilobular inflammatory infiltrates persisted up to 20 weeks. Perisinusoidal liver fibrosis was also increasingly detected in BALB/c mice, whereas no fibrous change was observed in nude mice after 6 weeks of Con A challenge. The number of stellate cells, detected by immunostaining, increased after 20 weeks of Con A injections. Liver cytokine messenger RNA (mRNA) expression after 20 weeks showed expression of transforming growth factor beta1 (TGF-beta1), IL-10, and IL-4 whereas IL-2 was no more expressed. The present study shows that mice repeatedly injected with Con A develop liver fibrosis. The cytokine-release pattern observed after 1 injection of Con A is rapidly shifted towards an immunomodulatory phenotype characterized by the systemic production of large amounts of IL-10.

Interleukin 10 reduces the incidence of pancreatitis after therapeutic endoscopic retrograde cholangiopancreatography.

BACKGROUND & AIMS: Prophylactic administration of interleukin (IL)-10 decreases the severity of experimental pancreatitis. Prevention of post-endoscopic retrograde cholangiopancreatography (ERCP) pancreatitis in humans is a unique model to study the potential role of IL-10 in this setting. METHODS: In a single-center, double-blind, randomized, placebo-controlled study, the effect of a single injection of 4 microg/kg (group 1) or 20 microg/kg (group 2) IL-10 was compared with that of placebo (group 0), all administered 30 minutes before therapeutic ERCP. The primary endpoint was the effect of IL-10 on serum levels of amylases and lipases measured 4, 24, and 48 hours after ERCP. The secondary objective was to evaluate changes in plasma cytokines (IL-6, IL-8, tumor necrosis factor) at the same time points and the incidence of acute pancreatitis in the 3 groups. Subjects undergoing a first therapeutic ERCP were eligible for inclusion. RESULTS: A total of 144 patients were included. Seven were excluded based on intention to treat (n = 1) or per protocol (n = 6). Forty-five, 48, and 44 patients remained in groups 0, 1, and 2, respectively. The 3 groups were comparable for age, sex, underlying disease, indication for treatment, type of treatment, and plasma levels of C-reactive protein (CRP), cytokines, and hydrolases at baseline. No significant difference was observed in CRP, cytokine, and hydrolase plasma levels after ERCP. Forty-three patients developed hyperhydrolasemia (18 in group 0, 14 in group 1, and 11 in group 2; P = 0.297), and 19 patients developed acute clinical pancreatitis (11 in group 0, 5 in group 1, 3 in group 2; P = 0.038). Two severe cases were observed in the placebo group. No mortality related to ERCP was observed. Logistic regression identified 3 independent risk factors for post-therapeutic ERCP pancreatitis: IL-10 administration (odds ratio [OR], 0.46; 95% confidence interval [95% CI], 0.22-0.96; P = 0.039), pancreatic sphincterotomy (OR, 5.04; 95% CI, 1.53-16.61; P = 0.008), and acinarization (OR, 8.19; 95% CI, 1.83-36.57; P = 0.006). CONCLUSIONS: A single intravenous dose of IL-10, given 30 minutes before the start of the procedure, independently reduces the incidence of post-therapeutic ERCP pancreatitis.