Simple and surprisingly effective one-step extraction-cleanup by Soxflo for DDT and its metabolites from environmental samples

A pilot study found that DDT breakdown at the GC inlet was extensive in extracts from some-but not all-samples with high organic carbon contents. However, DDT losses could be prevented with a one-step extraction-cleanup in the Soxflo instrument with dichloromethane and charcoal. This dry-column procedure took 1 h at room temperature. It was tested on spiked soil and peat samples and validated with certified soil and sediment reference materials. Spike recoveries from freshly spiked samples ranged from 79 to 111% at 20-4000 mug/kg concentrations. Recoveries from the real-world CRMs were 99.7-100.2% of DDT, 89.7-90.4% of DDD and 89.6-107.9% of DDE. It was concluded that charcoal cleanups should be used routinely during surveys for environmental DDX pollution in order to mitigate against unpredictable matrix-enhanced breakdown in the GC. (C) 2004 Elsevier B.V. All rights reserved.

A facile one step synthesis of N-2 substituted 3-phenyliminoisoindolinones from N-(2-carboxybenzoyl)-anthranilic acid and the design of reverse-turn mimetics

Stirring of N-(2-carboxybenzoyl) anthranilic acid with anilines and amines such as p-toluidine, benzylamine, methyl esters of Leu, Phe, Ile and Val in presence of DCC produces N- 2 substituted 3-phenyliminoisoindolinones in very good yields. Single crystal X-ray diffraction studies and solution phase NMR and CD studies reveal that the 3-phenyliminoisoindolinone moiety is a turn-inducing scaffold which should be useful for reverse-turn mimetics.

One-step catalytic cyclohexane oxidation to adipic acid using molecular oxygen

Using combination of Mn-Co transition metal species with N-hydroxyphthalimide as a catalyst for one-step oxidation of cyclohexane with molecular oxygen in acetic acid at 353 K can give more than 95% selectivity towards oxygenated products with adipic acid as a major product at a high conversion (ca. 78%). A turnover number of 74 for this partial oxidation are also recorded.

A stable one-step-ahead predictive control of non-linear systems

In this paper stability of one-step ahead predictive controllers based on non-linear models is established. It is shown that, under conditions which can be fulfilled by most industrial plants, the closed-loop system is robustly stable in the presence of plant uncertainties and input–output constraints. There is no requirement that the plant should be open-loop stable and the analysis is valid for general forms of non-linear system representation including the case out when the problem is constraint-free. The effectiveness of controllers designed according to the algorithm analyzed in this paper is demonstrated on a recognized benchmark problem and on a simulation of a continuous-stirred tank reactor (CSTR). In both examples a radial basis function neural network is employed as the non-linear system model.

One step forward, and two steps back: women and career progression in academia during times of uncertainty

While there is an extensive and still growing body of literature on women in academia and the challenges they encounter in career progression, there is little research on their experience specifically within a business school setting. In this study, we attempt to address this gap and examine the experiences and career development of female academics in a business school and how these are impacted by downsizing programmes. To this end, an exploratory case study is conducted. The findings of this study show that female business school academics experience numerous challenges in terms of promotion and development, networking, and the multiple and conflicting demands placed upon them. As a result, the lack of visibility seems to be a pertinent issue in terms of their career progression. Our data also demonstrates that that, paradoxically, during periods of downsizing women become more visible and thus vulnerable to layoffs as a consequence of the challenges and pressures created in their environment during this process. In this paper, we argue that this heightened visibility, and being subject to possible layoffs, further reproduces inequality regimes in academia.

National and sub-national assessments of soil organic carbon stocks and changes: The GEFSOC modelling system

Soil organic carbon (SOC) plays a vital role in ecosystem function, determining soil fertility, water holding capacity and susceptibility to land degradation. In addition, SOC is related to atmospheric CO, levels with soils having the potential for C release or sequestration, depending on land use, land management and climate. The United Nations Convention on Climate Change and its Kyoto Protocol, and other United Nations Conventions to Combat Desertification and on Biodiversity all recognize the importance of SOC and point to the need for quantification of SOC stocks and changes. An understanding of SOC stocks and changes at the national and regional scale is necessary to further our understanding of the global C cycle, to assess the responses of terrestrial ecosystems to climate change and to aid policy makers in making land use/management decisions. Several studies have considered SOC stocks at the plot scale, but these are site specific and of limited value in making inferences about larger areas. Some studies have used empirical methods to estimate SOC stocks and changes at the regional scale, but such studies are limited in their ability to project future changes, and most have been carried out using temperate data sets. The computational method outlined by the Intergovernmental Panel on Climate Change (IPCC) has been used to estimate SOC stock changes at the regional scale in several studies, including a recent study considering five contrasting eco regions. This 'one step' approach fails to account for the dynamic manner in which SOC changes are likely to occur following changes in land use and land management. A dynamic modelling approach allows estimates to be made in a manner that accounts for the underlying processes leading to SOC change. Ecosystem models, designed for site scale applications can be linked to spatial databases, giving spatially explicit results that allow geographic areas of change in SOC stocks to be identified. Some studies have used variations on this approach to estimate SOC stock changes at the sub-national and national scale for areas of the USA and Europe and at the watershed scale for areas of Mexico and Cuba. However, a need remained for a national and regional scale, spatially explicit system that is generically applicable and can be applied to as wide a range of soil types, climates and land uses as possible. The Global Environment Facility Soil Organic Carbon (GEFSOC) Modelling System was developed in response to this need. The GEFSOC system allows estimates of SOC stocks and changes to be made for diverse conditions, providing essential information for countries wishing to take part in an emerging C market, and bringing us closer to an understanding of the future role of soils in the global C cycle. (C) 2007 Elsevier B.V. All rights reserved.

Introduction of 4-chloro-alpha-cyanocinnamic acid liquid matrices for high sensitivity UV-MALDI MS

Matrix-assisted laser desorption/ionization (MALDI) is a key ionization technique in mass spectrometry (MS) for the analysis of labile macromolecules. An important area of study and improvements in relation to MALDI and its application in high-sensitivity MS is that of matrix design and sample preparation. Recently, 4-chloro-alpha-cyanocinnamic acid (ClCCA) has been introduced as a new rationally designed matrix and reported to provide an improved analytical performance as demonstrated by an increase in sequence coverage of protein digests obtained by peptide mass mapping (PMM) (Jaskolla, T. W.; et al. Proc. Natl. Acad. Sci. U.S.A. 2008, 105, 12200-12205). This new matrix shows the potential to be a superior alternative to the commonly used and highly successful alpha-cyano-4-hydroxycinnamic acid (CHCA). We have taken this design one step further by developing and optimizing an ionic liquid matrix (ILM) and liquid support matrix (LSM) using ClCCA as the principle chromophore and MALDI matrix compound. These new liquid matrices possess greater sample homogeneity and a simpler morphology. The data obtained from our studies show improved sequence coverage for BSA digests compared to the traditional CHCA crystalline matrix and for the ClCCA-containing ILM a similar performance to the ClCCA crystalline matrix down to 1 fmol of BSA digest prepared in a single MALDI sample droplet with current sensitivity levels in the attomole range. The LSMs show a high tolerance to contamination such as ammonium bicarbonate, a commonly used buffering agent.

A novel approach to processing high-performance polymers that exploits entropically driven ring-opening polymerization

Blends of the poly(ether sulfone) derived from 4,4'-biphenol and 4,4'-dichlorodiphenylsulfone (Radel-R(TM)) with its homologous macrocyclic oligomers show greatly lowered melt viscosities relative to that of the parent polymer, potentially enabling more facile production and fabrication of fiber-reinforced composite materials. The macrocycles can then undergo entropically driven ring-opening polymerization in situ. The required blends can be obtained easily in one step, by carrying out polycondensations at concentrations lower than those usually used for polymer synthesis.

Facile bisurethane supramolecular polymers containing flexible alicyclic receptor units

This paper details the synthesis, characterisation and physical analyses of a series of hydrogen bonded urethane supramolecular polymer systems that are created by a facile one-step synthesis from inexpensive and commercially available starting materials. We report the synthesis and characterisation of a series of low molecular weight bisurethanes (<650 a.m.u.) that exhibit physical properties in the bulk that are characteristic of polyurethane materials possessing far higher molecular weight. The physical characteristics of these low molecular weight bisurethanes were investigated by using temperature-dependent rheological analysis and viscometry and the nature in which these compounds assembled was assessed using IR and NMR spectroscopies. These studies reveal that these simple bisurethanes self-assemble via hydrogen bonding interactions.

Adaptive general predictive controller for nonlinear systems

A nonlinear general predictive controller (NLGPC) is described which is based on the use of a Hammerstein model within a recursive control algorithm. A key contribution of the paper is the use of a novel, one-step simple root solving procedure for the Hammerstein model, this being a fundamental part of the overall tuning algorithm. A comparison is made between NLGPC and nonlinear deadbeat control (NLDBC) using the same one-step nonlinear components, in order to investigate NLGPC advantages and disadvantages.

Rational expectations? Developer behaviour and development cycles in the central London office market

Purpose – Expectations of future market conditions are acknowledged to be crucial for the development decision and hence for shaping the built environment. The purpose of this paper is to study the central London office market from 1987 to 2009 and test for evidence of rational, adaptive and naive expectations. Design/methodology/approach – Two parallel approaches are applied to test for either rational or adaptive/naive expectations: vector auto-regressive (VAR) approach with Granger causality tests and recursive OLS regression with one-step forecasts. Findings – Applying VAR models and a recursive OLS regression with one-step forecasts, the authors do not find evidence of adaptive and naïve expectations of developers. Although the magnitude of the errors and the length of time lags between market signal and construction starts vary over time and development cycles, the results confirm that developer decisions are explained, to a large extent, by contemporaneous and historic conditions in both the City and the West End, but this is more likely to stem from the lengthy design, financing and planning permission processes rather than adaptive or naive expectations. Research limitations/implications – More generally, the results of this study suggest that real estate cycles are largely generated endogenously rather than being the result of large demand shocks and/or irrational behaviour. Practical implications – Developers may be able to generate excess profits by exploiting market inefficiencies but this may be hindered in practice by the long periods necessary for planning and construction of the asset. Originality/value – This paper focuses the scholarly debate of real estate cycles on the role of expectations. It is also one of very few spatially disaggregate studies of the subject matter.

"Oft expectation fails": a time-series analysis of construction starts in the London office market

Expectations of future market conditions are generally acknowledged to be crucial for the development decision and hence for shaping the built environment. This empirical study of the Central London office market from 1987 to 2009 tests for evidence of adaptive and naive expectations. Applying VAR models and a recursive OLS regression with one-step forecasts, we find evidence of adaptive and naïve, rather than rational expectations of developers. Although the magnitude of the errors and the length of time lags vary over time and development cycles, the results confirm that developers’ decisions are explained to a large extent by contemporaneous and past conditions in both London submarkets. The corollary of this finding is that developers may be able to generate excess profits by exploiting market inefficiencies but this may be hindered in practice by the long periods necessary for planning and construction of the asset. More generally, the results of this study suggest that real estate cycles are largely generated endogenously rather than being the result of unexpected exogenous shocks.

Fetal programming effects of testosterone on the reward system and behavioral approach tendencies in humans

BACKGROUND: Sex differences are present in many neuropsychiatric conditions that affect emotion and approach-avoidance behavior. One potential mechanism underlying such observations is testosterone in early development. Although much is known about the effects of testosterone in adolescence and adulthood, little is known in humans about how testosterone in fetal development influences later neural sensitivity to valenced facial cues and approach-avoidance behavioral tendencies. METHODS: With functional magnetic resonance imaging we scanned 25 8-11-year-old children while viewing happy, fear, neutral, or scrambled faces. Fetal testosterone (FT) was measured via amniotic fluid sampled between 13 and 20 weeks gestation. Behavioral approach-avoidance tendencies were measured via parental report on the Sensitivity to Punishment and Sensitivity to Rewards questionnaire. RESULTS: Increasing FT predicted enhanced selectivity for positive compared with negatively valenced facial cues in reward-related regions such as caudate, putamen, and nucleus accumbens but not the amygdala. Statistical mediation analyses showed that increasing FT predicts increased behavioral approach tendencies by biasing caudate, putamen, and nucleus accumbens but not amygdala to be more responsive to positive compared with negatively valenced cues. In contrast, FT was not predictive of behavioral avoidance tendencies, either through direct or neurally mediated paths. CONCLUSIONS: This work suggests that testosterone in humans acts as a fetal programming mechanism on the reward system and influences behavioral approach tendencies later in life. As a mechanism influencing atypical development, FT might be important across a range of neuropsychiatric conditions that asymmetrically affect the sexes, the reward system, emotion processing, and approach behavior.

Non-toxigenic Escherichia coli O157:H7 strain NCTC12900 causes attaching-effacing lesions and eae-dependent persistence in weaned sheep

Ruminants are regarded as a primary reservoir for Escherichia coli O157:H7, an important human pathogen. Intimin, encoded by the Locus of Enterocyte Effacement by E. coli O157:H7 organisms, has been cited as one bacterial mechanism of colonisation of the gastrointestinal tract. To confirm this and to test whether a non-toxigenic E. coli O157:H7 strain would colonise and persist in a sheep model, E. coli O157:H7 strain NCTC12900, that lacks Shiga toxin (stx) genes, was evaluated for use in a sheep model of persistence. Following oral inoculation of six-week-old sheep, persistent excretion of NCTC12900 was observed for up to 48 days. E. coli O157-associated attaching-effacing (AE) lesions were detected in the caecum and rectum of one six-week-old lamb, one day after inoculation. This is the first recorded observation of AE lesions in orally inoculated weaned sheep. Also, mean faecal excretion scores of NCTC12900 and an isogenic intimin (eae)-deficient mutant were determined from twenty-four six-week-old orally inoculated sheep. The eae mutant was cleared within 20 days and had lower mean excretion scores at all time points after day one post inoculation compared with the parental strain that was still being excreted at 48 days. Tissues were collected post mortem from animals selected at random from the study groups over the time course of the experiment. The eae mutant was detected in only 1/43 samples but the parental strain was recovered from 64/140 samples primarily from the large bowel although rumen, duodenum, jejunum, and ileum were culture positive especially from animals that were still excreting at and beyond 27 days after inoculation.

Isolation of recombinant antibodies against EspA and intimin of Escherichia coli O157:H7

Intimin, Tir, and EspA proteins are expressed by attaching-effacing Escherichia coli, which include enteropathogenic and enterohemorrhagic E. coli pathotypes. EspA proteins are part of the type three secretion system needle complex that delivers Tir to the host epithelial cell, while surface arrayed intimin docks the bacterium to the translocated Tir. This intimate attachment leads to attaching and effacing lesions. Recombinant forms of these effector proteins from enterohemorrhagic E. coli O157:H7 were produced by using E. coli expression vectors. Binding of intimin and Tir fragments in enzyme-linked immunosorbent assay (ELISAs) demonstrated the interaction of intimin fragments containing the C-terminal 282 or 188 amino acids to a Tir fragment containing amino acid residues 258 to 361. Recombinant intimin and EspA proteins were used to elicit immune responses in rabbits and immune phage-display antibody libraries were produced. Screening of these immune libraries by conventional phage-antibody panning and colony filter screening produced a panel of antibodies with specificity for EspA or intimin. Antibodies recognizing different C-terminal epitopes on intimin bound specifically to the gamma intimin of O157:H7 and not to other classes of intimin. Antibodies recognizing EspA from E. coli O157 also recognized the protein from the eae-deficient O157 mutant DM3 and from E. coli O111. Anti-intimin antibodies were also produced as fusion proteins coupled to the reporter molecule alkaline phosphatase, allowing the one-step detection of gamma intimin. The isolated recombinant monoclonal antibodies were functional in a range of assay formats, including ELISA, Western blotting, and dot blots, thus demonstrating their diagnostic potential.