Effects of plant sulfur nutrition on acrylamide and aroma compounds in cooked wheat

Wheat flour from plants deficient in sulfur has been shown to contain substantially higher levels of free amino acids, particularly asparagine and glutamine, than flour from wheat grown where sulfur nutrition was sufficient. Elevated levels of asparagine resulted in acrylamide levels up to 6 times higher in sulfur-deprived wheat flour, compared with sulfur-sufficient wheat flour, for three varieties of winter wheat. The volatile compounds from flour, heated at 180 degrees C for 20 min, have been compared for these three varieties of wheat grown with and without sulfur fertilizer. Approximately 50 compounds were quantified in the headspace extracts of the heated flour; over 30 compounds were affected by sulfur fertilization, and 15 compounds were affected by variety. Unsaturated aldehydes formed from aldol condensations, Strecker. aldehydes, alkylpyrazines, and low molecular weight alkylfurans were found at higher concentrations in the sulfur-deficient flour, whereas low molecular weight pyrroles and thiophenes and sugar breakdown products were found at higher concentrations in the sulfur-sufficient flour. The reasons for these differences and the relationship between acrylamide formation and aroma volatile formation are discussed.

Protocol for the PINCER trial: a cluster randomised trial comparing the effectiveness of a pharmacist-led IT-based intervention with simple feedback in reducing rates of clinically important errors in medicines management in general practices

Background: Medication errors are an important cause of morbidity and mortality in primary care. The aims of this study are to determine the effectiveness, cost effectiveness and acceptability of a pharmacist-led information-technology-based complex intervention compared with simple feedback in reducing proportions of patients at risk from potentially hazardous prescribing and medicines management in general (family) practice. Methods: Research subject group: "At-risk" patients registered with computerised general practices in two geographical regions in England. Design: Parallel group pragmatic cluster randomised trial. Interventions: Practices will be randomised to either: (i) Computer-generated feedback; or (ii) Pharmacist-led intervention comprising of computer-generated feedback, educational outreach and dedicated support. Primary outcome measures: The proportion of patients in each practice at six and 12 months post intervention: - with a computer-recorded history of peptic ulcer being prescribed non-selective non-steroidal anti-inflammatory drugs - with a computer-recorded diagnosis of asthma being prescribed beta-blockers - aged 75 years and older receiving long-term prescriptions for angiotensin converting enzyme inhibitors or loop diuretics without a recorded assessment of renal function and electrolytes in the preceding 15 months. Secondary outcome measures; These relate to a number of other examples of potentially hazardous prescribing and medicines management. Economic analysis: An economic evaluation will be done of the cost per error avoided, from the perspective of the UK National Health Service (NHS), comparing the pharmacist-led intervention with simple feedback. Qualitative analysis: A qualitative study will be conducted to explore the views and experiences of health care professionals and NHS managers concerning the interventions, and investigate possible reasons why the interventions prove effective, or conversely prove ineffective. Sample size: 34 practices in each of the two treatment arms would provide at least 80% power (two-tailed alpha of 0.05) to demonstrate a 50% reduction in error rates for each of the three primary outcome measures in the pharmacist-led intervention arm compared with a 11% reduction in the simple feedback arm. Discussion: At the time of submission of this article, 72 general practices have been recruited (36 in each arm of the trial) and the interventions have been delivered. Analysis has not yet been undertaken.

Ferric and ferrous iron in nitroso-myoglobin: computer simulations of stable and metastable states and their infrared spectra

The binding of NO to iron is involved in the biological function of many heme proteins. Contrary to ligands like CO and O-2, which only bind to ferrous (Fe-II) iron, NO binds to both ferrous and ferric (Fe-II) iron. In a particular protein, the natural oxidation state can therefore be expected to be tailored to the required function. Herein, we present an ob initio potential-energy surface for ferric iron interacting with NO. This potential-energy surface exhibits three minima corresponding to eta'-NO coordination (the global minimum), eta(1)-ON coordination and eta(2) coordination. This contrasts with the potential-energy surface for Fe-II-NO, which ex- hibits only two minima (the eta(2) coordination mode for Fe-II is a transition state, not a minimum). In addition, the binding energies of NO are substantially larger for Fe-III than for Fe-II. We have performed molecular dynamics simulations for NO bound to ferric myoglobin (Mb(III)) and compare these with results obtained for Mb(II). Over the duration of our simulations (1.5 ns), all three binding modes are found to be stable at 200 K and transiently stable at 300 K, with eventual transformation to the eta(1)-NO global-minimum conformation. We discuss the implication of these results related to studies of rebinding processes in myoglobin.

A phosphorus analogue of Bis(eta(4)-cyclobutadiene)iron(0)

Iron is a pivotal element in organometallic chemistry, enabling fundamental insights with high-impact applications.[1] Ferrocene derivatives have countless uses,[2] and the recent advances in iron catalysis are equally impressive.[3]

Assessing the impact of nano- and micro-scale zerovalent iron particles on soil microbial activities: Particle reactivity interferes with assay conditions and interpretation of genuine microbial effects

The effects of nano-scale and micro-scale zerovalent iron (nZVI and mZVI) particles on general (dehydrogenase and hydrolase) and specific (ammonia oxidation potential, AOP) activities mediated by the microbial community in an uncontaminated soil were examined. nZVI (diameter 12.5 nm; 10 mg gÿ1 soil)apparently inhibited AOP and nZVI and mZVI apparently stimulated dehydrogenase activity but had minimal influence on hydrolase activity. Sterile experiments revealed that the apparent inhibition of AOP could not be interpreted as such due to the confounding action of the particles, whereas, the nZVIenhanced dehydrogenase activity could represent the genuine response of a stimulated microbial population or an artifact of ZVI reactivity. Overall, there was no evidence for negative effects of nZVI or mZVI on the processes studied. When examining the impact of redox active particles such as ZVI on microbial oxidation–reduction reactions, potential confounding effects of the test particles on assay conditions should be considered.

Redox control of light-induced charge separation in a transition metal cluster: photochemistry of a methyl viologen-substituted [Os-3(CO)10(a-diimine)] cluster

Sub)picosecond transient absorption (TA) and time-resolved infrared (TRIR) spectra of the cluster [OS3(CO)(10-) (AcPy-MV)](2+) (the clication AcPy-MV = Acpy-MV2+ = [2-pyridylacetimine-N-(2-(1'-methyl-4,4'-bipyridine-1,1'-diium-1-yl) ethyl)] (PF6)(2)) (1(2+)) reveal that photoinduced electron transfer to the electron-accepting 4,4'-bipyridine-1,1'diium (MV2+) moiety competes with the fast relaxation of the initially populated sigmapi* excited state of the cluster to the ground state and/or cleavage of an Os-Os bond. The TA spectra of cluster 12 in acetone, obtained by irradiation into its lowest-energy absorption band, show the characteristic absorptions of the one-electron-reduced MV*(+) unit at 400 and 615 nm, in accordance with population of a charge-separated (CS) state in which a cluster-core electron has been transferred to the lowest pi* orbital of the remote MV2+ unit. This assignment is confirmed by picosecond TRIR spectra that show a large shift of the pilot highest-frequency nu(CO) band of 1(2+) by ca. +40 cm(-1), reflecting the photooxidation of the cluster core. The CS state is populated via fast (4.2 x 10(11) s(-1)) and efficient (88%) oxidative quenching of the optically populated sigmapi* excited state and decays biexponentially with lifetimes of 38 and 166 ps (1:2:1 ratio) with a complete regeneration of the parent cluster. About 12% of the cluster molecules in the sigmapi* excited state form long-lived open-core biradicals. In strongly coordinating acetonitrile, however, the cluster core-to-MV2+ electron transfer in cluster 12+ results in the irreversible formation of secondary photoproducts with a photooxidized cluster core. The photochemical behavior of the [Os-3(CO)(10)(alpha-diimine-MV)](2+) (donor-acceptor) dyad can be controlled by an externally applied electronic bias. Electrochemical one-electron reduction of the MV2+ moiety prior to the irradiation reduces its electron-accepting character to such an extent that the photoinduced electron transfer to MV*+ is no longer feasible. Instead, the irradiation of reduced cluster 1(.)+ results in the reversible formation of an open-core zwitterion, the ultimate photoproduct also observed upon irradiation of related nonsubstituted clusters [Os-3(CO)(10)(alpha-diimine)] in strongly coordinating solvents such as acetonitrile.

Syntheses, structures, some reactions, and electrochemical oxidation of ferrocenylethynyl complexes of iron, ruthenium, and osmium

The syntheses and characterizations of several complexes containing ferrocenylethynyl and ferrocene-1,1'-bis(ethynyl) groups attached to M(PP)Cp'[M = Fe, Ru, PP = dppe, Cp'= Cp*; M = Ru, Os, PP = (PPh3)(2), dppe, Cp' = Cp] are described. Reactions with tetracyanoethene have given either tetracyanobuta-1,3-dienyl or eta(3)-allylic derivatives, while addition of Me+ afforded the corresponding vinylidene derivatives. Some electrochemical measurements are discussed in terms of electronic communication between the redox-active M(PP)Cp' groups through the ferrocene nucleus. The molecular structures of 14 of these complexes have been determined by crystallographic methods.

Intelligent agents for fault tolerance: from multi-agent simulation to cluster-based implementation

Recent research in multi-agent systems incorporate fault tolerance concepts, but does not explore the extension and implementation of such ideas for large scale parallel computing systems. The work reported in this paper investigates a swarm array computing approach, namely 'Intelligent Agents'. A task to be executed on a parallel computing system is decomposed to sub-tasks and mapped onto agents that traverse an abstracted hardware layer. The agents intercommunicate across processors to share information during the event of a predicted core/processor failure and for successfully completing the task. The feasibility of the approach is validated by simulations on an FPGA using a multi-agent simulator, and implementation of a parallel reduction algorithm on a computer cluster using the Message Passing Interface.

A cluster-based implementation of a fault-tolerant parallel reduction algorithm using swarm-array computing

Recent research in multi-agent systems incorporate fault tolerance concepts. However, the research does not explore the extension and implementation of such ideas for large scale parallel computing systems. The work reported in this paper investigates a swarm array computing approach, namely ‘Intelligent Agents’. In the approach considered a task to be executed on a parallel computing system is decomposed to sub-tasks and mapped onto agents that traverse an abstracted hardware layer. The agents intercommunicate across processors to share information during the event of a predicted core/processor failure and for successfully completing the task. The agents hence contribute towards fault tolerance and towards building reliable systems. The feasibility of the approach is validated by simulations on an FPGA using a multi-agent simulator and implementation of a parallel reduction algorithm on a computer cluster using the Message Passing Interface.

The use of trajectory cluster analysis to interpret trace gas measurements at Mace Head, Ireland

A first step in interpreting the wide variation in trace gas concentrations measured over time at a given site is to classify the data according to the prevailing weather conditions. In order to classify measurements made during two intensive field campaigns at Mace Head, on the west coast of Ireland, an objective method of assigning data to different weather types has been developed. Air-mass back trajectories calculated using winds from ECMWF analyses, arriving at the site in 1995–1997, were allocated to clusters based on a statistical analysis of the latitude, longitude and pressure of the trajectory at 12 h intervals over 5 days. The robustness of the analysis was assessed by using an ensemble of back trajectories calculated for four points around Mace Head. Separate analyses were made for each of the 3 years, and for four 3-month periods. The use of these clusters in classifying ground-based ozone measurements at Mace Head is described, including the need to exclude data which have been influenced by local perturbations to the regional flow pattern, for example, by sea breezes. Even with a limited data set, based on 2 months of intensive field measurements in 1996 and 1997, there are statistically significant differences in ozone concentrations in air from the different clusters. The limitations of this type of analysis for classification and interpretation of ground-based chemistry measurements are discussed.

Multivariable cluster analysis for high-speed industrial machinery

The overall operation and internal complexity of a particular production machinery can be depicted in terms of clusters of multidimensional points which describe the process states, the value in each point dimension representing a measured variable from the machinery. The paper describes a new cluster analysis technique for use with manufacturing processes, to illustrate how machine behaviour can be categorised and how regions of good and poor machine behaviour can be identified. The cluster algorithm presented is the novel mean-tracking algorithm, capable of locating N-dimensional clusters in a large data space in which a considerable amount of noise is present. Implementation of the algorithm on a real-world high-speed machinery application is described, with clusters being formed from machinery data to indicate machinery error regions and error-free regions. This analysis is seen to provide a promising step ahead in the field of multivariable control of manufacturing systems.

Isolation and characterisation of EfeM, a periplasmic component of the putative EfeUOBM iron transporter of Pseudomonas syringae pv. syringae

The EfeM protein is a component of the putative EfeUOBM iron-transporter of Pseudomonas syringae pathovar syringae and is thought to act as a periplasmic, ferrous-iron binding protein. It contains a signal peptide of 34 amino acid residues and a C-terminal 'Peptidase_M75' domain of 251 residues. The C-terminal domain contains a highly conserved 'HXXE' motif thought to act as part of a divalent cation-binding site. In this work, the gene (efeM or 'Psyr_3370') encoding EfeM was cloned and over-expressed in Escherichia coli, and the mature protein was purified from the periplasm. Mass spectrometry confirmed the identity of the protein (M(W) 27,772Da). Circular dichroism spectroscopy of EfeM indicated a mainly alpha-helical structure, consistent with bioinformatic predictions. Purified EfeM was crystallised by hanging-drop vapor diffusion to give needle-shaped crystals that diffracted to a resolution of 1.6A. This is the first molecular study of a peptidase M75 domain with a presumed iron transport role.