Multistep π dimerization of tetrakis(n-decyl)heptathienoacene radical cations: a combined experimental and theoretical study

Radical cations of a heptathienoacene a,b-substituted with four n-decyl side groups (D4T7C+) form exceptionally stable p-dimer dications already at ambient temperature (Chem. Comm. 2011, 47, 12622). This extraordinary p-dimerization process is investigated here with a focus on the ultimate[D4T7C+]2 p-dimer dication and yet-unreported transitoryspecies formed during and after the oxidation. To this end, we use a joint experimental and theoretical approach that combines cyclic voltammetry, in situ spectrochemistry and spectroelectrochemistry, EPR spectroscopy, and DFT calculations. The impact of temperature, thienoacene concentration, and the nature and concentration of counteranions on the p-dimerization process is also investigated in detail. Two different transitory species were detected in the course of the one-electron oxidation: 1) a different transient conformation of the ultimate [D4T7C+]2 p-dimer dications, the stability of which is strongly affected by the applied experimental conditions, and 2) intermediate [D4T7]2C+ p-dimer radical cations formed prior to the fully oxidized [D4T7]2C+ p-dimer dications. Thus, this comprehensive work demonstrates the formation of peculiar supramolecular species of heptathienoacene radical cations, the stability, nature, and structure of which have been successfully analyzed. We therefore believe that this study leads to a deeper fundamental understanding of the mechanism of dimer formation between conjugated aromatic systems.

Identification and quantification of glucosinolate and flavonol compounds in rocket salad (Eruca sativa, Eruca vesicaria and Diplotaxis tenuifolia) by LC–MS: Highlighting the potential for improving nutritional value of rocket crops

Liquid Chromatography Mass Spectrometry (LC-MS) was used to obtain glucosinolate and flavonol content for 35 rocket accessions and commercial varieties. 13 glucosinolates and 11 flavonol compounds were identified. Semi-quantitative methods were used to estimate concentrations of both groups of compounds. Minor glucosinolate composition was found to be different between accessions; concentrations varied significantly. Flavonols showed differentiation between genera, with Diplotaxis accumulating quercetin glucosides and Eruca accumulating kaempferol glucosides. Several compounds were detected in each genus that have only previously been reported in the other. We highlight how knowledge of phytochemical content and concentration can be used to breed new, nutritionally superior varieties. We also demonstrate the effects of controlled environment conditions on the accumulations of glucosinolates and flavonols and explore the reasons for differences with previous studies. We stress the importance of consistent experimental design between research groups to effectively compare and contrast results.

Centennial changes in the solar wind speed and in the open solar flux

We use combinations of geomagnetic indices, based on both variation range and hourly means, to derive the solar wind flow speed, the interplanetary magnetic field strength at 1 AU and the total open solar flux between 1895 and the present. We analyze the effects of the regression procedure and geomagnetic indices used by adopting four analysis methods. These give a mean interplanetary magnetic field strength increase of 45.1 ± 4.5% between 1903 and 1956, associated with a 14.4 ± 0.7% rise in the solar wind speed. We use averaging timescales of 1 and 2 days to allow for the difference between the magnetic fluxes threading the coronal source surface and the heliocentric sphere at 1 AU. The largest uncertainties originate from the choice of regression procedure: the average of all eight estimates of the rise in open solar flux is 73.0 ± 5.0%, but the best procedure, giving the narrowest and most symmetric distribution of fit residuals, yields 87.3 ± 3.9%.

Modeling the observed proton aurora and ionospheric convection responses to changes in the IMF clock angle: 1. Persistence of cusp proton aurora

We employ a numerical model of cusp ion precipitation and proton aurora emission to fit variations of the peak Doppler-shifted Lyman-a intensity observed on 26 November 2000 by the SI-12 channel of the FUV instrument on the IMAGE satellite. The major features of this event appeared in response to two brief swings of the interplanetary magnetic field (IMF) toward a southward orientation. We reproduce the observed spatial distributions of this emission on newly opened field lines by combining the proton emission model with a model of the response of ionospheric convection. The simulations are based on the observed variations of the solar wind proton temperature and concentration and the interplanetary magnetic field clock angle. They also allow for the efficiency, sampling rate, integration time and spatial resolution of the FUV instrument. The good match (correlation coefficient 0.91, significant at the 98% level) between observed and modeled variations confirms the time constant (about 4 min) for the rise and decay of the proton emissions predicted by the model for southward IMF conditions. The implications for the detection of pulsed magnetopause reconnection using proton aurora are discussed for a range of interplanetary conditions.

Ionospheric and geomagnetic responses to changes in IMF B_Z: a superposed epoch study

Superposed epoch studies have been carried out in order to determine the ionospheric response at mid-latitudes to southward turnings of the interplanetary magnetic field (IMF). This is compared with the geomagnetic response, as seen in the indices K p, AE and Dst. The solar wind, IMF and geomagnetic data used were hourly averages from the years 1967–1989 and thus cover a full 22-year cycle in the solar magnetic field. These data were divided into subsets, determined by the magnitudes of the southward turnings and the concomitant increase in solar wind pressure. The superposed epoch studies were carried out using the time of the southward turning as time zero. The response of the mid-latitude ionosphere is studied by looking at the F-layer critical frequencies, f o F2, from hourly soundings by the Slough ionosonde and their deviation from the monthly median values, δf o F2. For the southward turnings with a change in B z of δB z > 11.5 nT accompanied by a solar wind dynamic pressure P exceeding 5 nPa, the F region critical frequency, f o F2, shows a marked decrease, reaching a minimum value about 20 h after the southward turning. This recovers to pre-event values over the subsequent 24 h, on average. The Dst index shows the classic storm-time decrease to about −60 nT. Four days later, the index has still to fully recover and is at about −25 nT. Both the K p and AE indices show rises before the southward turnings, when the IMF is strongly northward but the solar wind dynamic pressure is enhanced. The average AE index does register a clear isolated pulse (averaging 650 nT for 2 h, compared with a background peak level of near 450 nT at these times) showing enhanced energy deposition at high latitudes in substorms but, like K p, remains somewhat enhanced for several days, even after the average IMF has returned to zero after 1 day. This AE background decays away over several days as the Dst index recovers, indicating that there is some contamination of the currents observed at the AE stations by the continuing enhanced equatorial ring current. For data averaged over all seasons, the critical frequencies are depressed at Slough by 1.3 MHz, which is close to the lower decile of the overall distribution of δf o Fl values. Taking 30-day periods around summer and winter solstice, the largest depression is 1.6 and 1.2 MHz, respectively. This seasonal dependence is confirmed by a similar study for a Southern Hemisphere station, Argentine Island, giving peak depressions of 1.8 MHz and 0.5 MHz for summer and winter. For the subset of turnings where δB z > 11.5 nT and P ≤ 5 nPa, the response of the geomagnetic indices is similar but smaller, while the change in δf o F2 has all but disappeared. This confirms that the energy deposited at high latitudes, which leads to the geomagnetic and ionospheric disturbances following a southward turning of the IMF, increases with the energy density (dynamic pressure) of the solar wind flow. The magnitude of all responses are shown to depend on δB z . At Slough, the peak depression always occurs when Slough rotates into the noon sector. The largest ionospheric response is for southward turnings seen between 15–21 UT.

Effects of organic and conventional fertilizer treatments on host selection by the aphid parasitoid Diaeretiella rapae

The type and quantity of fertilizer supplied to a crop will differ between organic and conventional farming practices. Altering the type of fertilizer a plant is provided with can influence a plant’s foliar nitrogen levels, as well as the composition and concentration of defence compounds, such as glucosinolates. Many natural enemies of insect herbivores can respond to headspace volatiles emitted by the herbivores’ host plant in response to herbivory. We propose that manipulating fertilizer type may also influence the headspace volatile profiles of plants, and as a result, the tritrophic interactions that occur between plants, their insect pests and those pests’ natural enemies. Here, we investigate a tritrophic system consisting of cabbage plants, Brassica oleracea, a parasitoid, Diaeretiella rapae, and one of its hosts, the specialist cabbage aphid Brevicoryne brassicae. Brassica oleracea plants were provided with either no additional fertilization or one of three types of fertilizer: Nitram (ammonium nitrate), John Innes base or organic chicken manure. We investigated whether these changes would alter the rate of parasitism of aphids on those plants and whether any differences in parasitism could be explained by differences in attractivity of the plants to D. rapae or attack rate of aphids by D. rapae. In free-choice experiments, there were significant differences in the percentage of B. brassicae parasitized by D. rapae between B. oleracea plants grown in different fertilizer treatments. In a series of dual-choice Y-tube olfactometry experiments, D. rapae females discriminated between B. brassicae-infested and undamaged plants, but parasitoids did not discriminate between similarly infested plants grown in different fertilizer treatments. Correspondingly, in attack rate experiments, there were no differences in the rate that D. rapae attacked B. brassicae on B. oleracea plants grown in different fertilizer treatments. These findings are of direct relevance to sustainable and conventional farming practices.

Terrestrial exposure of oilfield flowline additives diminish soil structural stability and remediative microbial function

Onshore oil production pipelines are major installations in the petroleum industry, stretching many thousands of kilometres worldwide which also contain flowline additives. The current study focuses on the effect of the flowline additives on soil physico-chemical and biological properties and quantified the impact using resilience and resistance indices. Our findings are the first to highlight deleterious effect of flowline additives by altering some fundamental soil properties, including a complete loss of structural integrity of the impacted soil and a reduced capacity to degrade hydrocarbons mainly due to: (i) phosphonate salts (in scale inhibitor) prevented accumulation of scale in pipelines but also disrupted soil physical structure; (ii) glutaraldehyde (in biocides) which repressed microbial activity in the pipeline and reduced hydrocarbon degradation in soil upon environmental exposure; (iii) the combinatory effects of these two chemicals synergistically caused severe soil structural collapse and disruption of microbial degradation of petroleum hydrocarbons.

Scoring rules and competitive behavior in best value construction auctions

This paper examines the extent to which engineers can influence the competitive behavior of bidders in Best Value or multi-attribute construction auctions, where both the (dollar) bid and technical non-price criteria are scored according to a scoring rule. From a sample of Spanish construction auctions with a variety of bid scoring rules, it is found that bidders are influenced by the auction rules in significant and predictable ways. The bid score weighting, bid scoring formula and abnormally low bid criterion are variables likely to influence the competitiveness of bidders in terms of both their aggressive/conservative bidding and concentration/dispersion of bids. Revealing the influence of the bid scoring rules and their magnitude on bidders’ competitive behavior opens the door for the engineer to condition bidder competitive behavior in such a way as to provide the balance needed to achieve the owner’s desired strategic outcomes.

Variability and trends in Laptev Sea ice outflow between 1992-2011

Variability and trends in seasonal and interannual ice area export out of the Laptev Sea between 1992 and 2011 are investigated using satellite-based sea ice drift and concentration data. We found an average total winter (Octo- ber to May) ice area transport across the northern and east- ern Laptev Sea boundaries (NB and EB) of 3.48 × 10 5 km 2 . The average transport across the NB (2.87 × 10 5 km 2 ) is thereby higher than across the EB (0.61 × 10 5 km 2 ), with a less pronounced seasonal cycle. The total Laptev Sea ice area flux significantly increased over the last decades (0.85 × 10 5 km 2 decade − 1 , p> 0 . 95), dominated by increas- ing export through the EB (0.55 × 10 5 km 2 decade − 1 , p> 0 . 90), while the increase in export across the NB is smaller (0.3 × 10 5 km 2 decade − 1 ) and statistically not significant. The strong coupling between across-boundary SLP gradient and ice drift velocity indicates that monthly variations in ice area flux are primarily controlled by changes in geostrophic wind velocities, although the Laptev Sea ice circulation shows no clear relationship with large-scale atmospheric in- dices. Also there is no evidence of increasing wind velocities that could explain the overall positive trends in ice export. The increased transport rates are rather the consequence of a changing ice cover such as thinning and/or a decrease in con- centration. The use of a back-propagation method revealed that most of the ice that is incorporated into the Transpolar Drift is formed during freeze-up and originates from the cen- tral and western part of the Laptev Sea, while the exchange with the East Siberian Sea is dominated by ice coming from the central and southeastern Laptev Sea. Furthermore, our re- sults imply that years of high ice export in late winter (Febru- ary to May) have a thinning effect on the ice cover, which in turn preconditions the occurence of negative sea ice extent anomalies in summer.

Colloidal gas aphrons based separation process for the purification and fractionation of natural phenolic extracts

Following previous studies, the aim of this work is to further investigate the application of colloidal gas aphrons (CGA) to the recovery of polyphenols from a grape marc ethanolic extract with particular focus on exploring the use of a non-ionic food grade surfactant (Tween 20) as an alternative to the more toxic cationic surfactant CTAB. Different batch separation trials in a flotation column were carried out to evaluate the influence of surfactant type and concentration and processing parameters (such as pH, drainage time, CGA/extract volumetric and molar ratio) on the recovery of total and specific phenolic compounds. The possibility of achieving selective separation and concentration of different classes of phenolic compounds and non-phenolic compounds was also assessed, together with the influence of the process on the antioxidant capacity of the recovered compounds. The process led to good recovery, limited loss of antioxidant capacity, but low selectivity under the tested conditions. Results showed the possibility of using Tween 20 with a separation mechanism mainly driven by hydrophobic interactions. Volumetric ratio rather than the molar ratio was the key operating parameter in the recovery of polyphenols by CGA.

Riparian shading controls instream spring phytoplankton and benthic diatom growth

Dissolved oxygen (DO) concentrations showed a striking pattern in a multi-year study of the River Enborne, a small river in SE England. In each of three years (2010-2012), maximum DO concentrations were attained in mid-April, preceded by a period of steadily increasing diurnal amplitudes, followed by a steady reduction in both amplitude and concentration. Flow events during the reduction period reduce DO to low concentrations until the following spring. Evidence is presented that this pattern is mainly due to benthic algal growth which is eventually supressed by the growth of the riparian tree canopy. Nitrate and silicate concentrations are too high to inhibit the growth of either benthic algae or phytoplankton, but phosphate concentrations might have started to reduce growth if the tree canopy development had been delayed. This interpretation is supported by evidence from weekly flow cytometry measurements and analysis of the diurnal, seasonal and annual patterns of nutrient concentrations. As the tree canopy develops, the river switches from an autotrophic to a heterotrophic state. The results support the use of riparian shading to help control algal growth, and highlight the risks of reducing riparian shade.

Naturally occurring radioactive material (NORM) from a former phosphoric acid processing plant

In recent years there has been an increasing awareness of the radiological impact of non-nuclear industries that extract and/or process ores and minerals containing naturally occurring radioactive material (NORM). These industrial activities may result in significant radioactive contamination of (by-) products, wastes and plant installations. In this study, scale samples were collected from a decommissioned phosphoric acid processing plant. To determine the nature and concentration of NORM retained in pipe-work and associated process plant, four main areas of the site were investigated: (1) the 'Green Acid Plant', where crude acid was concentrated; (2) the green acid storage tanks; (3) the Purified White Acid (PWA) plant, where inorganic impurities were removed; and (4) the solid waste, disposed of on-site as landfill. The scale samples predominantly comprise the following: fluorides (e.g. ralstonite); calcium sulphate (e.g. gypsum); and an assemblage of mixed fluorides and phosphates (e.g. iron fluoride hydrate, calcium phosphate), respectively. The radioactive inventory is dominated by U-238 and its decay chain products, and significant fractionation along the series occurs. Compared to the feedstock ore, elevated concentrations (<= 8.8 Bq/g) of U-238 Were found to be retained in installations where the process stream was rich in fluorides and phosphates. In addition, enriched levels (<= 11 Bq/g) of Ra-226 were found in association with precipitates of calcium sulphate. Water extraction tests indicate that many of the scales and waste contain significantly soluble materials and readily release radioactivity into solution. (c) 2005 Elsevier Ltd. All rights reserved.

The influence of hilly terrain on canopy-atmosphere carbon dioxide exchange

Topography influences many aspects of forest-atmosphere carbon exchange; yet only a small number of studies have considered the role of topography on the structure of turbulence within and above vegetation and its effect on canopy photosynthesis and the measurement of net ecosystem exchange of CO2 (N-ee) using flux towers. Here, we focus on the interplay between radiative transfer, flow dynamics for neutral stratification, and ecophysiological controls on CO2 sources and sinks within a canopy on a gentle cosine hill. We examine how topography alters the forest-atmosphere CO2 exchange rate when compared to uniform flat terrain using a newly developed first-order closure model that explicitly accounts for the flow dynamics, radiative transfer, and nonlinear eco physiological processes within a plant canopy. We show that variation in radiation and airflow due to topography causes only a minor departure in horizontally averaged and vertically integrated photosynthesis from their flat terrain values. However, topography perturbs the airflow and concentration fields in and above plant canopies, leading to significant horizontal and vertical advection of CO2. Advection terms in the conservation equation may be neglected in flow over homogeneous, flat terrain, and then N-ee = F-c, the vertical turbulent flux of CO2. Model results suggest that vertical and horizontal advection terms are generally of opposite sign and of the same order as the biological sources and sinks. We show that, close to the hilltop, F-c departs by a factor of three compared to its flat terrain counterpart and that the horizontally averaged F-c-at canopy top differs by more than 20% compared to the flat-terrain case.

Nectar resource diversity organises flower-visitor community structure

Communities of nectar-producing plants show high spatio-temporal variation in the patterns of volume and concentration presentation. We illustrate a novel approach for quantifying nectar reward structures in complex communities, demonstrating that nectar resource diversity (defined as the variety of nectar volume-concentration combinations available) may be a fundamental factor organising nectarivore communities. In a series of diverse bee and entomophilous flower communities in Israel, our measure of nectar resource diversity alone explains the majority of variation in bee species richness, while other nectar variables (volume, concentration, energy value, and water content) have little predictive value per se. The new measure of nectar resource diversity is highly correlated with floral species richness and particularly with the species richness of annuals, yet it is additive in its effect on bee diversity. We conclude that relying solely upon measurements of mean nectar volume and mean nectar concentration overlooks a key characteristic of community-level reward structure, nectar resource diversity, so that previous studies may have failed to identify an important determinant of flower-visitor community structure.

Colonic metabolism of dietary polyphenols: influence of structure on microbial fermentation products

The metabolism of chlorogenic acid., naringin, and rutin, representative members of three common families of dietary polyphenols, the hydroxycinnamates, the flavanones, and the flavonols, respectively, was studied in an in vitro mixed culture model of the human colonic microflora. Time- and concentration-dependent degradation of all three compounds was observed, which was associated with the following metabolic events after cleavage of the ester or glycosidic bond: reduction of the aliphatic double bond of the resulting hydroxycinnamate caffeic acid residue; dehydroxylation and ring fission of the heterocyclic C-ring of the resulting deglycosylated flavanone, naringenin, and of the deglycosylated flavonol, quercetin (which differed depending on the substitution). The metabolic events, their sequences, and major phenolic end products, as identified by GC-MS or LC-MS/MS, were elucidated from the structural characteristics of the investigated compounds. The major phenolic end products identified were 3-D-hydroxyphenyl)propionic acid for chlorogenic acid, 3-(4-hydroxyphenyl)-propionic acid and 3-phenylpropionic acid for naringin, and 3-hydroxyphenylacetic acid and 3-(3-hydroxyphenyl)-propionic acid for rutin. The degree of degradation of the compounds studied was significantly influenced by the substrate concentration as well as individual variations in the composition of the fecal flora. The results support extensive metabolism of dietary polyphenols in the colon, depending on substrate concentration and residence time, with resultant formation of simple phenolics, which can be considered biomarkers of colonic metabolism if subsequently absorbed. It is also apparent that a relatively small number of phenolic degradation products are formed in the colon from the diverse group of natural polyphenols. (C) 2003 Elsevier Inc. All rights reserved.