Quantitative analysis of the reactivity of formate species seen by DRIFTS over a Au/Ce(La)O2 water–gas shift catalyst: First unambiguous evidence of the minority role of formates as reaction intermediates

The reactivity of the species formed at the surface of a Au/Ce(La)O2 catalyst during the water������¢���¯���¿���½���¯���¿���½gas shift (WGS) reaction were investigated by operando diffuse reflectance Fourier transform spectroscopy (DRIFTS) at the chemical steady state during isotopic transient kinetic analyses (SSITKA). The exchanges of the reaction product CO2 and of formate and carbonate surface species were followed during an isotopic exchange of the reactant CO using a DRIFTS cell as a single reactor. The DRIFTS cell was a modified commercial cell that yielded identical reaction rates to that measured over a quartz plug-flow reactor. The DRIFTS signal was used to quantify the relative oncentrations of the surface species and CO2. The analysis of the formate exchange curves between 428 and 493 K showed that at least two levels of reactivity were present. ������¢���¯���¿���½���¯���¿���½Slow formates������¢���¯���¿���½���¯���¿���½ displayed an exchange rate constant 10- to 20-fold slower than that of the reaction product CO2. ������¢���¯���¿���½���¯���¿���½Fast formates������¢���¯���¿���½���¯���¿���½ were exchanged on a time scale similar to that of CO2. Multiple nonreactive readsorption of CO2 took place, accounting for the kinetics of the exchange of CO2(g) and making it impossible to determine the number of active sites through the SSITKA technique. The concentration (in mol g������¢���¯���¿���½���¯���¿���½1) of formates on the catalyst was determined through a calibration curve and allowed calculation of the specific rate of formate decomposition. The rate of CO2 formation was more than an order of magnitude higher than the rate of decomposition of formates (slow + fast species), indicating that all of the formates detected by DRIFTS could not be the main reaction intermediates in the production of CO2. This work stresses the importance of full quantitative analyses (measuring both rate constants and adsorbate concentrations) when investigating the role of adsorbates as potential reaction intermediates, and illustrates how even reactive species seen by DRIFTS may be unimportant in the overall reaction scheme.

First report of a novel plant lysozyme with both antifungal and antibacterial activities.

A novel lysozyme exhibiting antifungal activity and with a molecular mass of 14.4 kDa in SDS–polyacrylamide gel electrophoresis was isolated from mung bean (Phaseolus mungo) seeds using a procedure that involved aqueous extraction, ammonium sulfate precipitation, ion exchange chromatography on CM-Sephadex, and high-performance liquid chromatography on POROS HS-20. Its N-terminal sequence was very different from that of hen egg white lysozyme. Its pI was estimated to be above 9.7. The specific activity of the lysozyme was 355 U/mg at pH 5.5 and 30 °C. The lysozyme exhibited a pH optimum at pH 5.5 and a temperature optimum at 55 °C. It is reported herein, for the first time, that a novel plant lysozyme exerted an antifungal action toward Fusarium oxysporum, Fusarium solani, Pythium aphanidermatum, Sclerotium rolfsii, and Botrytis cinerea, in addition to an antibacterial action against Staphylococcus aureus.

Time operators for one parameter semigroups

We develop two simple approaches to the construction of time operators for semigroups of continuous linear operators in Hilbert spaces provided that the generators of these semigroups are normal operators. The first approach enables us to give explicit formulas (in the spectral representations) both for the time operators and for their eigenfunctions. The other approach provides no explicit formula. However, it enables us to find necessary and sufficient conditions for the existence of time operators for semigroups of continuous linear operators in separable Hilbert spaces with normal generators. Time superoperators corresponding to unitary groups are also discussed.

The PRIME 1996 cruise: an overview

The UK PRIME cruise, June-July 1996 in the NE Atlantic, consisted of two legs. During the first, detailed chemical and biological observations were made in time-series mode adjacent to the centre of a cold-core eddy in the vicinity of 59 degreesN 20 degreesW using SF6 tracer techniques as the basis for the Lagrangian study. The eddy, which appeared to have been formed the previous winter, remained coherent over the 9 days of the survey and advected only slowly. The phytoplankton community in the eddy was dominated by the coccolithophorid Coccolithus huxleyi. High microzooplankton grazing rates indicated minimal export losses from the surface layer. Significant shifts in many, but not all, of the chemical and biological properties measured were observed over the course of the experiment, especially after the passage of a storm event, which resulted in considerable deepening of the mixed layer followed by a return to fully stratified conditions. The second leg consisted of a transect from 59 degreesN 20 degreesW to 37 degreesN 19 degreesW, with a further Lagrangian time-series study based on a drogue marker initiated at the southern end of the transect. Maximal biological activity was generally encountered in the region between two fronts located at 52.5 degreesN and 48 degreesN, while to the south of 48 degreesN oligotrophic conditions prevailed. At the southern Lagrangian site, a deep chlorophyll maximum was present and high column new production was recorded as a result of the euphotic zone extending below the depth of the nutricline. Microzooplankton grazing rates were lower at this location than at the northern eddy site. The influx of a warm, saline water body into the upper layers during the southern survey led to a major shift in many of the biological and chemical properties being measured. At both the northern and southern Lagrangian sites, the biomass of the mesozooplankton exceeded that of the microzooplankton. (C) 2001 Elsevier Science Ltd. All rights reserved.

Ultrafast Laser-Driven Excitation Dynamics in Ne: An Ab Initio Time-Dependent R-Matrix Approach

An attosecond pump-probe scheme that combines the use of a free-electron laser pulse with an ultrashort pulse is applied in order to explore the ultrafast excitation dynamics in Ne. We describe the multielectron dynamics using a new nonperturbative time-dependent R-matrix theory. This theory enables the interaction of ultrashort light fields with multielectron atoms and atomic ions to be determined from first principles. By probing the emission of an inner 2s electron from Ne we are also able to study the bound state population dynamics during the free-electron laser pulse.

Right-left discrimination among medical students: Getting it right all of the time?

Objective To determine medical students’ self awareness and ability to discriminate right from left; to identify characteristics associated with this ability; and to identify any techniques used to aid discrimination. Design Questionnaire and psychometric study. Setting Undergraduate medical school, Northern Ireland. Participants 290 first year undergraduate students. Main outcome measure Medical students’ ability to discriminate right from left using the Bergen right-left discrimination test. Results Test scores ranged from 31 to 143 on a scale of 0- 144 (mean 112 (standard deviation 22.2)). Male students significantly outperformed female students (117.18 (26.96) v 110.80 (28.94)). Students who wanted to be surgeons performed significantly better than those who wanted to be general practitioners or medical doctors (119.87 (25.15) v 110.55 (27.36) v 112.50 (26.88)). The interaction effect for sex and career wishes was not significant (P=0.370). Students who used learnt techniques to help them discriminate scored significantly less than those who did not (P

Reduced-complexity iterative equalization for severe time-dispersive MIMO channels

In this paper, a reduced-complexity soft-interference-cancellation minimum mean-square-error.(SIC-MMSE) iterative equalization method for severe time-dispersive multiple-input-multiple-output (MIMO) channels is proposed. To mitigate the severe time dispersiveness of the channel, a single carrier with cyclic prefix is employed, and the equalization is per-formed in the frequency domain. This simplifies the challenging problem of equalization in MIMO channels due to both the intersymbol interference (ISI) and the coantenna interference (CAI). The proposed iterative algorithm works in two stages. The first stage estimates the transmitted frequency-domain symbols using a low-complexity SIC-MMSE equalizer. The second stage converts the estimated frequency-domain symbols in the time domain and finds their means and variances to incorporate in the SIC-MMSE equalizer in the next iteration. Simulation results show the bit-/symbol-error-rate performance of the SIC-MMSE equalizer, with and without coding, for various modulation schemes.

Host-based P2P flow identification and use in real-time

Data identification is a key task for any Internet Service Provider (ISP) or network administrator. As port fluctuation and encryption become more common in P2P traffic wishing to avoid identification, new strategies must be developed to detect and classify such flows. This paper introduces a new method of separating P2P and standard web traffic that can be applied as part of a data mining process, based on the activity of the hosts on the network. Unlike other research, our method is aimed at classifying individual flows rather than just identifying P2P hosts or ports. Heuristics are analysed and a classification system proposed. The accuracy of the system is then tested using real network traffic from a core internet router showing over 99% accuracy in some cases. We expand on this proposed strategy to investigate its application to real-time, early classification problems. New proposals are made and the results of real-time experiments compared to those obtained in the data mining research. To the best of our knowledge this is the first research to use host based flow identification to determine a flows application within the early stages of the connection.

First dielectronic recombination measurements with H-like uranium

In this report we show first results on dielectronic recombination (DR) measurements with H-like uranium U91+. The experiments were conducted at the heavy ion storage ring ESR of GSI. The electron cooler of the ESR was used as a target for free electrons. Stochastic pre-cooling of the stored ion beam was employed in order to accomplish high-energy resolution at the necessary high electron-ion collision energies of more than 64 keV. For the DR of U91+ this novel technique enabled us to measure for the first time the KLL-DR process and even to resolve the individual j-j' fine structure components of the KLjLj' resonances. The experimental data are compared with fully relativistic Multi-Configuration Dirac-Fock (DR-MCDF) calculations. (c) 2006 Elsevier Ltd. All rights reserved.

Efficient Evaluation of Multidimensional Time-Varying Density Forecasts

We propose two simple evaluation methods for time varying density forecasts of continuous higher dimensional random variables. Both methods are based on the probability integral transformation for unidimensional forecasts. The first method tests multinormal densities and relies on the rotation of the coordinate system. The advantage of the second method is not only its applicability to any continuous distribution but also the evaluation of the forecast accuracy in specific regions of its domain as defined by the user’s interest. We show that the latter property is particularly useful for evaluating a multidimensional generalization of the Value at Risk. In simulations and in an empirical study, we examine the performance of both tests.

GALEX AND PAN-STARRS1 DISCOVERY OF SN IIP 2010aq: THE FIRST FEW DAYS AFTER SHOCK BREAKOUT IN A RED SUPERGIANT STAR

We present the early UV and optical light curve of Type IIP supernova (SN) 2010aq at z = 0.0862, and compare it to analytical models for thermal emission following SN shock breakout in a red supergiant star. SN 2010aq was discovered in joint monitoring between the Galaxy Evolution Explorer (GALEX) Time Domain Survey (TDS) in the NUV and the Pan-STARRS1 Medium Deep Survey (PS1 MDS) in the g, r, i, and z bands. The GALEX and Pan-STARRS1 observations detect the SN less than 1 day after the shock breakout, measure a diluted blackbody temperature of 31,000 +/- 6000 K 1 day later, and follow the rise in the UV/optical light curve over the next 2 days caused by the expansion and cooling of the SN ejecta. The high signal-to-noise ratio of the simultaneous UV and optical photometry allows us to fit for a progenitor star radius of 700 +/- 200R(circle dot), the size of a red supergiant star. An excess in UV emission two weeks after shock breakout compared with SNe well fitted by model atmosphere-code synthetic spectra with solar metallicity is best explained by suppressed line blanketing due to a lower metallicity progenitor star in SN 2010aq. Continued monitoring of PS1 MDS fields by the GALEX TDS will increase the sample of early UV detections of Type II SNe by an order of magnitude and probe the diversity of SN progenitor star properties.

Animal-borne sensors successfully capture the real-time thermal properties of ocean basins

Climate change is perhaps the most pressing and urgent environmental issue facing the world today. However our ability to predict and quantify the consequences of this change is severely limited by the paucity of in situ oceanographic measurements. Marine animals equipped with sophisticated oceanographic data loggers to study their behavior offer one solution to this problem because marine animals range widely across the world's ocean basins and visit remote and often inaccessible locations. However, unlike the information being collected from conventional oceanographic sensing equipment, which has been validated, the data collected from instruments deployed on marine animals over long periods has not. This is the first long-term study to validate in situ oceanographic data collected by animal oceanographers. We compared the ocean temperatures collected by leatherback turtles (Dermochelys coriacea) in the Atlantic Ocean with the ARGO network of ocean floats and could find no systematic errors that could be ascribed to sensor instability. Animal-borne sensors allowed water temperature to be monitored across a range of depths, over entire ocean basins, and, importantly, over long periods and so will play a key role in assessing global climate change through improved monitoring of global temperatures. This finding is especially pertinent given recent international calls for the development and implementation of a comprehensive Earth observation system ( see http://iwgeo.ssc.nasa.gov/documents.asp?s=review) that includes the use of novel techniques for monitoring and understanding ocean and climate interactions to address strategic environmental and societal needs.

Time of flight mass spectrometry for quantitative data analysis in fast transient studies using a Temporal Analysis of Products (TAP) reactor

A Time of flight (ToF) mass spectrometer suitable in terms of sensitivity, detector response and time resolution, for application in fast transient Temporal Analysis of Products (TAP) kinetic catalyst characterization is reported. Technical difficulties associated with such application as well as the solutions implemented in terms of adaptations of the ToF apparatus are discussed. The performance of the ToF was validated and the full linearity of the specific detector over the full dynamic range was explored in order to ensure its applicability for the TAP application. The reported TAP-ToF setup is the first system that achieves the high level of sensitivity allowing monitoring of the full 0-200 AMU range simultaneously with sub-millisecond time resolution. In this new setup, the high sensitivity allows the use of low intensity pulses ensuring that transport through the reactor occurs in the Knudsen diffusion regime and that the data can, therefore, be fully analysed using the reported theoretical TAP models and data processing.

Intermittent versus continuous oxaliplatin and fluoropyrimidine combination chemotherapy for first-line treatment of advanced colorectal cancer: results of the randomised phase 3 MRC COIN trial

Background: When cure is impossible, cancer treatment should focus on both length and quality of life. Maximisation of time without toxic effects could be one effective strategy to achieve both of these goals. The COIN trial assessed preplanned treatment holidays in advanced colorectal cancer to achieve this aim. Methods: COIN was a randomised controlled trial in patients with previously untreated advanced colorectal cancer. Patients received either continuous oxaliplatin and fluoropyrimidine combination (arm A), continuous chemotherapy plus cetuximab (arm B), or intermittent (arm C) chemotherapy. In arms A and B, treatment continued until development of progressive disease, cumulative toxic effects, or the patient chose to stop. In arm C, patients who had not progressed at their 12-week scan started a chemotherapy-free interval until evidence of disease progression, when the same treatment was restarted. Randomisation was done centrally (via telephone) by the MRC Clinical Trials Unit using minimisation. Treatment allocation was not masked. The comparison of arms A and B is described in a companion paper. Here, we compare arms A and C, with the primary objective of establishing whether overall survival on intermittent therapy was non-inferior to that on continuous therapy, with a predefined non-inferiority boundary of 1·162. Intention-to-treat (ITT) and per-protocol analyses were done. This trial is registered, ISRCTN27286448. Findings: 1630 patients were randomly assigned to treatment groups (815 to continuous and 815 to intermittent therapy). Median survival in the ITT population (n=815 in both groups) was 15·8 months (IQR 9·4—26·1) in arm A and 14·4 months (8·0—24·7) in arm C (hazard ratio [HR] 1·084, 80% CI 1·008—1·165). In the per-protocol population (arm A, n=467; arm C, n=511), median survival was 19·6 months (13·0—28·1) in arm A and 18·0 months (12·1—29·3) in arm C (HR 1·087, 0·986—1·198). The upper limits of CIs for HRs in both analyses were greater than the predefined non-inferiority boundary. Preplanned subgroup analyses in the per-protocol population showed that a raised baseline platelet count, defined as 400 000 per µL or higher (271 [28%] of 978 patients), was associated with poor survival with intermittent chemotherapy: the HR for comparison of arm C and arm A in patients with a normal platelet count was 0·96 (95% CI 0·80—1·15, p=0·66), versus 1·54 (1·17—2·03, p=0·0018) in patients with a raised platelet count (p=0·0027 for interaction). In the per-protocol population, more patients on continuous than on intermittent treatment had grade 3 or worse haematological toxic effects (72 [15%] vs 60 [12%]), whereas nausea and vomiting were more common on intermittent treatment (11 [2%] vs 43 [8%]). Grade 3 or worse peripheral neuropathy (126 [27%] vs 25 [5%]) and hand—foot syndrome (21 [4%] vs 15 [3%]) were more frequent on continuous than on intermittent treatment. Interpretation: Although this trial did not show non-inferiority of intermittent compared with continuous chemotherapy for advanced colorectal cancer in terms of overall survival, chemotherapy-free intervals remain a treatment option for some patients with advanced colorectal cancer, offering reduced time on chemotherapy, reduced cumulative toxic effects, and improved quality of life. Subgroup analyses suggest that patients with normal baseline platelet counts could gain the benefits of intermittent chemotherapy without detriment in survival, whereas those with raised baseline platelet counts have impaired survival and quality of life with intermittent chemotherapy and should not receive a treatment break.

Using simulation to assess cardiac first-responder schemes exhibiting stochastic and spatial complexities

A Monte-Carlo simulation-based model has been constructed to assess a public health scheme involving mobile-volunteer cardiac First-Responders. The scheme being assessed aims to improve survival of Sudden-Cardiac-Arrest (SCA) patients, through reducing the time until administration of life-saving defibrillation treatment, with volunteers being paged to respond to possible SCA incidents alongside the Emergency Medical Services. The need for a model, for example, to assess the impact of the scheme in different geographical regions, was apparent upon collection of observational trial data (given it exhibited stochastic and spatial complexities). The simulation-based model developed has been validated and then used to assess the scheme's benefits in an alternative rural region (not a part of the original trial). These illustrative results conclude that the scheme may not be the most efficient use of National Health Service resources in this geographical region, thus demonstrating the importance and usefulness of simulation modelling in aiding decision making.