Simultaneous bridge-localized and mixed-valence character in diruthenium radical cations featuring diethynylaromatic bridging ligands

A series of bimetallic ruthenium complexes [{Ru(dppe)Cp*}2(μ-C≡CArC≡C)] featuring diethynylaromatic bridging ligands (Ar = 1,4-phenylene, 1,4-naphthylene, 9,10-anthrylene) have been prepared and some representative molecular structures determined. A combination of UV–vis–NIR and IR spectroelectrochemical methods and density functional theory (DFT) have been used to demonstrate that one-electron oxidation of compounds [{Ru(dppe)Cp*}2(μ-C≡CArC≡C)](HC≡CArC≡CH = 1,4-diethynylbenzene; 1,4-diethynyl-2,5-dimethoxybenzene; 1,4-diethynylnaphthalene; 9,10-diethynylanthracene) yields solutions containing radical cations that exhibit characteristics of both oxidation of the diethynylaromatic portion of the bridge, and a mixed-valence state. The simultaneous population of bridge-oxidized and mixed-valence states is likely related to a number of factors, including orientation of the plane of the aromatic portion of the bridging ligand with respect to the metal d-orbitals of appropriate π-symmetry.

Determination of turbulent heat fluxes using a large aperture scintillometer over undulating mixed agricultural terrain

Scintillometry is an established technique for determining large areal average sensible heat fluxes. The scintillometer measurement is related to sensible heat flux via Monin–Obukhov similarity theory, which was developed for ideal homogeneous land surfaces. In this study it is shown that judicious application of scintillometry over heterogeneous mixed agriculture on undulating topography yields valid results when compared to eddy covariance (EC). A large aperture scintillometer (LAS) over a 2.4 km path was compared with four EC stations measuring sensible (H) and latent (LvE) heat fluxes over different vegetation (cereals and grass) which when aggregated were representative of the LAS source area. The partitioning of available energy into H and LvE varied strongly for different vegetation types, with H varying by a factor of three between senesced winter wheat and grass pasture. The LAS derived H agrees (one-to-one within the experimental uncertainty) with H aggregated from EC with a high coefficient of determination of 0.94. Chronological analysis shows individual fields may have a varying contribution to the areal average sensible heat flux on short (weekly) time scales due to phenological development and changing soil moisture conditions. Using spatially aggregated measurements of net radiation and soil heat flux with H from the LAS, the areal averaged latent heat flux (LvELAS) was calculated as the residual of the surface energy balance. The regression of LvELAS against aggregated LvE from the EC stations has a slope of 0.94, close to ideal, and demonstrates that this is an accurate method for the landscape-scale estimation of evaporation over heterogeneous complex topography.

In vitro fermentation of lactulose-derived oligosaccharides by mixed fecal microbiota

Fermentation properties of oligosaccharides derived from lactulose (OsLu) and lactose (GOS) have been assessed in pH-controlled anaerobic batch cultures using lactulose and Vivinal-GOS as reference carbohydrates. Changes in gut bacterial populations and their metabolic activities were monitored over 24 h by fluorescent in situ hybridization (FISH) and by measurement of short-chain fatty acid (SCFA) production. Lactulose-derived oligosaccharides were selectively fermented by Bifidobacterium and lactic acid bacterial populations producing higher SCFA concentrations compared to GOS. The highest total SCFA production was from Vivinal-GOS > lactulose > OsLu > GOS. Longer incubation periods produced a selective fermentation of OsLu when they were used as a carbon source reaching the highest selective index scores. The new oligosaccharides may constitute a good alternative to lactulose, and they could belong to a new generation of prebiotics to be used as a functional ingredient for improving the composition of gut microflora.

Wind-driven mixing below the oceanic mixed layer

This study describes the turbulent processes in the upper ocean boundary layer forced by a constant surface stress in the absence of the Coriolis force using large-eddy simulation. The boundary layer that develops has a two-layer structure, a well-mixed layer above a stratified shear layer. The depth of the mixed layer is approximately constant, whereas the depth of the shear layer increases with time. The turbulent momentum flux varies approximately linearly from the surface to the base of the shear layer. There is a maximum in the production of turbulence through shear at the base of the mixed layer. The magnitude of the shear production increases with time. The increase is mainly a result of the increase in the turbulent momentum flux at the base of the mixed layer due to the increase in the depth of the boundary layer. The length scale for the shear turbulence is the boundary layer depth. A simple scaling is proposed for the magnitude of the shear production that depends on the surface forcing and the average mixed layer current. The scaling can be interpreted in terms of the divergence of a mean kinetic energy flux. A simple bulk model of the boundary layer is developed to obtain equations describing the variation of the mixed layer and boundary layer depths with time. The model shows that the rate at which the boundary layer deepens does not depend on the stratification of the thermocline. The bulk model shows that the variation in the mixed layer depth is small as long as the surface buoyancy flux is small.

Minimum norm regularization of descriptor systems by mixed output feedback

We study the regularization problem for linear, constant coefficient descriptor systems Ex' = Ax+Bu, y1 = Cx, y2 = Γx' by proportional and derivative mixed output feedback. Necessary and sufficient conditions are given, which guarantee that there exist output feedbacks such that the closed-loop system is regular, has index at most one and E+BGΓ has a desired rank, i.e., there is a desired number of differential and algebraic equations. To resolve the freedom in the choice of the feedback matrices we then discuss how to obtain the desired regularizing feedback of minimum norm and show that this approach leads to useful results in the sense of robustness only if the rank of E is decreased. Numerical procedures are derived to construct the desired feedback gains. These numerical procedures are based on orthogonal matrix transformations which can be implemented in a numerically stable way.

An assessment of the MODIS collection 5 leaf area index product for a region of mixed coniferous forest

Canopy leaf area index (LAI), defined as the single-sided leaf area per unit ground area, is a quantitative measure of canopy foliar area. LAI is a controlling biophysical property of vegetation function, and quantifying LAI is thus vital for understanding energy, carbon and water fluxes between the land surface and the atmosphere. LAI is routinely available from Earth Observation (EO) instruments such as MODIS. However EO-derived estimates of LAI require validation before they are utilised by the ecosystem modelling community. Previous validation work on the MODIS collection 4 (c4) product suggested considerable error especially in forested biomes, and as a result significant modification of the MODIS LAI algorithm has been made for the most recent collection 5 (c5). As a result of these changes the current MODIS LAI product has not been widely validated. We present a validation of the MODIS c5 LAI product over a 121 km2 area of mixed coniferous forest in Oregon, USA, based on detailed ground measurements which we have upscaled using high resolution EO data. Our analysis suggests that c5 shows a much more realistic temporal LAI dynamic over c4 values for the site we examined. We find improved spatial consistency between the MODIS c5 LAI product and upscaled in situ measurements. However results also suggest that the c5 LAI product underestimates the upper range of upscaled in situ LAI measurements.

Mixed copper, silver, and gold cyanides, (MxM′1–x)CN: tailoring chain structures to influence physical properties

Binary mixed-metal variants of the one-dimensional MCN compounds (M = Cu, Ag, and Au) have been prepared and characterized using powder X-ray diffraction, vibrational spectroscopy, and total neutron diffraction. A solid solution with the AgCN structure exists in the (CuxAg1–x)CN system over the range (0 ≤ x ≤ 1). Line phases with compositions (Cu1/2Au1/2)CN, (Cu7/12Au5/12)CN, (Cu2/3Au1/3)CN, and (Ag1/2Au1/2)CN, all of which have the AuCN structure, are found in the gold-containing systems. Infrared and Raman spectroscopies show that complete ordering of the type [M–C≡N–M′–N≡C−]n occurs only in (Cu1/2Au1/2)CN and (Ag1/2Au1/2)CN. The sense of the cyanide bonding was determined by total neutron diffraction to be [Ag–NC–Au–CN−]n in (Ag1/2Au1/2)CN and [Cu–NC–Au–CN−]n in (Cu1/2Au1/2)CN. In contrast, in (Cu0.50Ag0.50)CN, metal ordering is incomplete, and strict alternation of metals does not occur. However, there is a distinct preference (85%) for the N end of the cyanide ligand to be bonded to copper and for Ag–CN–Cu links to predominate. Contrary to expectation, aurophilic bonding does not appear to be the controlling factor which leads to (Cu1/2Au1/2)CN and (Ag1/2Au1/2)CN adopting the AuCN structure. The diffuse reflectance, photoluminescence, and 1-D negative thermal expansion (NTE) behaviors of all three systems are reported and compared with those of the parent cyanide compounds. The photophysical properties are strongly influenced both by the composition of the individual chains and by how such chains pack together. The NTE behavior is also controlled by structure type: the gold-containing mixed-metal cyanides with the AuCN structure show the smallest contraction along the chain length on heating.

Evidence for insertional codemixing: mixed compounds and French nominal groups in Brussels Dutch

In this paper we analyse mixed compounds, such as legume+winkel ‘vegetable shop, greengrocery’ and winter+paletot ‘winter coat’ which contain a French and a Dutch element, and French nominal groups, such as carte d’identité ‘identity card’, and journal parlé ‘radio news’, which bilingual speakers from Brussels frequently insert into Brussels Dutch utterances. Using Muysken’s (2000) typology of bilingual speech, we claim that the mixed compounds and the nominal groups display the characteristics of insertional code-mixing. In addition, some evidence for the existence of a continuum between borrowing and code-switching can be obtained from these examples. As the multimorphemic units that are inserted into Dutch are neither single words, nor full constituents, their status in the lexicon raises interesting issues for researchers interested in the interface between syntax and the lexicon (see also Backus 2003). We try to argue that nominal groups such as carte d’identité and journal parlé are probably best seen as lexical templates or constructional idioms (Booij, 2002b). The insertion of French constructional idioms in Brussels Dutch represents an innovation in the lexical patterns that are available to speakers of this language, which is highly relevant for theories of language change.

Elevated CO2 enrichment induces a differential biomass response in a mixed species temperate forest plantation

• In a free-air CO2 enrichment study (BangorFACE) Alnus glutinosa, Betula pendula and Fagus sylvatica were planted in areas of one, two and three species mixtures (n=4). The trees were exposed to ambient or elevated CO2 (580 µmol mol-1) for four years, and aboveground growth characteristics measured. • In monoculture, the mean effect of CO2 enrichment on aboveground woody biomass was +29, +22 and +16% for A. glutinosa, F. sylvatica, and B. pendula respectively. When the same species were grown in polyculture, the response to CO2 switched to +10, +7 and 0%, for A. glutinosa, B. pendula, and F. sylvatica respectively. • In ambient atmosphere our species grown in polyculture increased aboveground woody biomass from 12.9 ± 1.4 kg m-2 to 18.9 ± 1.0 kg m-2, whereas in an elevated CO2 atmosphere aboveground woody biomass increased from 15.2 ± 0.6 kg m-2 to 20.2 ± 0.6 kg m-2. The overyielding effect of polyculture was smaller (+7%) in elevated CO2 than in an ambient atmosphere (+18%). • Our results show that the aboveground response to elevated CO2 is significantly affected by intra- and inter-specific competition, and that elevated CO2 response may be reduced in forest communities comprised of tree species with contrasting functional traits.

On the attribution of stratospheric ozone and temperature changes to changes in ozone-depleting substances and well-mixed greenhouse gases

The vertical profile of global-mean stratospheric temperature changes has traditionally represented an important diagnostic for the attribution of the cooling effects of stratospheric ozone depletion and CO2 increases. However, CO2-induced cooling alters ozone abundance by perturbing ozone chemistry, thereby coupling the stratospheric ozone and temperature responses to changes in CO2 and ozone-depleting substances (ODSs). Here we untangle the ozone-temperature coupling and show that the attribution of global-mean stratospheric temperature changes to CO2 and ODS changes (which are the true anthropogenic forcing agents) can be quite different from the traditional attribution to CO2 and ozone changes. The significance of these effects is quantified empirically using simulations from a three-dimensional chemistry-climate model. The results confirm the essential validity of the traditional approach in attributing changes during the past period of rapid ODS increases, although we find that about 10% of the upper stratospheric ozone decrease from ODS increases over the period 1975–1995 was offset by the increase in CO2, and the CO2-induced cooling in the upper stratosphere has been somewhat overestimated. When considering ozone recovery, however, the ozone-temperature coupling is a first-order effect; fully 2/5 of the upper stratospheric ozone increase projected to occur from 2010–2040 is attributable to CO2 increases. Thus, it has now become necessary to base attribution of global-mean stratospheric temperature changes on CO2 and ODS changes rather than on CO2 and ozone changes.

Dispersal of soil-dwelling clover root weevil (Sitona lepidus Gyllenhal, Coleoptera: Curculionidae) larvae in mixed plant communities

Insect pests that have a root-feeding larval stage often cause the most sustained damage to plants because their attrition remains largely unseen, preventing early diagnosis and treatment. Characterising movement and dispersal patterns of subterranean insects is inherently difficult due to the difficulty in observing their behaviour. Our understanding of dispersal and movement patterns of soil-dwelling insects is therefore limited compared to above ground insect pests and tends to focus on vertical movements within the soil profile or assessments of coarse movement patterns taken from soil core measurements in the field. The objective of this study was to assess how the dispersal behaviour of the clover root weevil (CRW), Sitona lepidus larvae was affected by differing proportions of host (clover) and non-host (grass) plants under different soil water contents (SWC). This was undertaken in experimental mini-swards that allowed us to control plant community structure and soil water content. CRW larval survival was not affected either by white clover content or planting pattern or SWC in either experiment; however, lower clover composition in the sward resulted in CRW larvae dispersing further from where they hatched. Because survival was the same regardless of clover density, the proportion of infested plants was highest in sward boxes with the fewest clover plants (i.e. the low host plant density). Thus, there is potential for clover plants over a larger area to be colonised when the clover content of the sward is low.

Hepatitis C virus NS5A inhibits mixed lineage kinase 3 to block apoptosis

Hepatitis C virus (HCV) infection results in the activation of numerous stress responses including oxidative stress, with the potential to induce an apoptotic state. Previously we have shown that HCV attenuates the stress-induced, p38MAPK-mediated up-regulation of the K+ channel Kv2.1, to maintain the survival of infected cells in the face of cellular stress. We demonstrated that this effect was mediated by HCV non-structural 5A (NS5A) protein, which impaired p38MAPK activity through a polyproline motif dependent interaction, resulting in reduction of phosphorylation activation of Kv2.1. In this study, we investigated the host cell proteins targeted by NS5A in order to mediate Kv2.1 inhibition. We screened a phage-display library expressing the entire complement of human SH3 domains for novel NS5A-host cell interactions. This analysis identified mixed lineage kinase 3 (MLK3) as a putative NS5A interacting partner. MLK3 is a serine/threonine protein kinase that is a member of the MAPK kinase kinase (MAP3K) family and activates p38MAPK. An NS5A-MLK3 interaction was confirmed by co-immunoprecipitation and western blot analysis. We further demonstrate a novel role of MLK3 in the modulation of Kv2.1 activity, whereby MLK3 overexpression leads to the up-regulation of channel activity. Accordingly, coexpression of NS5A suppressed this stimulation. Additionally we demonstrate that overexpression of MLK3 induced apoptosis which was also counteracted by NS5A. We conclude that NS5A targets MLK3 with multiple downstream consequences for both apoptosis and K+ homeostasis.

Macroeconomic forecasting with mixed-frequency data: forecasting output growth in the United States

Many macroeconomic series, such as U.S. real output growth, are sampled quarterly, although potentially useful predictors are often observed at a higher frequency. We look at whether a mixed data-frequency sampling (MIDAS) approach can improve forecasts of output growth. The MIDAS specification used in the comparison uses a novel way of including an autoregressive term. We find that the use of monthly data on the current quarter leads to significant improvement in forecasting current and next quarter output growth, and that MIDAS is an effective way to exploit monthly data compared with alternative methods.