Iron catalysts for selective anti-Markovnikov alkene hydrosilylation using tertiary silanes

Alkene hydrosilylation, the addition of a silicon hydride (Si-H) across a carbon-carbon double bond, is one of the largest-scale industrial applications of homogeneous catalysis and is used in the commercial production of numerous consumer goods. For decades, precious metals, principally compounds of platinum and rhodium, have been used as catalysts for this reaction class. Despite their widespread application, limitations such as high and volatile catalyst costs and competing side reactions have persisted. Here, we report that well-characterized molecular iron coordination compounds promote the selective anti-Markovnikov addition of sterically hindered, tertiary silanes to alkenes under mild conditions. These Earth-abundant base-metal catalysts, coordinated by optimized bis(imino)pyridine ligands, show promise for industrial application.     

Progress of the comparative MHC Committee and a summary of the Comparative MHC Workshops held at the 32nd ISAG, Edinburgh and the 9th IVIS, Tokyo, 2010

The comparative MHC Nomenclature Committee was formed following a recommendation by the International Society for Animal Genetics (ISAG) at its meeting in G?ttingen, Germany in 2002. The committee subsequently became affiliated to VIC, the Veterinary Immunology Committee of IUIS; the International Union of Immunological Societies, which is the umbrella organization for immunology societies worldwide. The committee currently fulfils three roles: (1) to establish guidelines for MHC nomenclature in species outside of human and mouse, (2) to facilitate the development of databases which provide a source of validated MHC sequences with official nomenclatures for associated species (immuno-polymorphism database IPD-MHC) and (3) to facilitate scientific discussion on comparative aspects of MHC biology. The committee currently comprises individuals representing a range of species nomenclature committees. This report summarises progress the committee has made in addressing its core objectives as well as the principal outputs from the Comparative MHC Workshops held at the 32nd International Society for Animal Genetics (ISAG) conference in Edinburgh, UK in July 2010 as well as in August 2010 at the 9th International Veterinary Immunology Symposium (IVIS) in Tokyo, Japan. Additional data from posters and presentations at related workshops focussing on aspects of MHC biology are also included where appropriate.     

Prednisolone therapy for atopic dermatitis is less effective in dogs with lower pretreatment serum 25-hydroxyvitamin D concentrations

Serum 25-hydroxyvitamin D [25(OH)D] concentrations were measured in 20 dogs with atopic dermatitis prior to treatment with a standard therapeutic dosage of prednisolone (0.93-1.06 mg/kg) every other day for 5 weeks after 7 days of treatment with the same dosage once daily. The severity of their physical signs was scored before and 6 weeks after prednisolone treatment by the canine atopic dermatitis extent and severity index version 3 (CADESI-03) and the Edinburgh Pruritus Scale (EPS). The 20 dogs with atopic dermatitis that were treated with prednisolone did not have significantly lower serum concentrations of 25(OH)D than a group of 36 healthy dogs, and the physical severity of the atopic dermatitis was not correlated to pretreatment serum 25(OH)D concentrations. However, dogs which had a marked improvement of their physical signs, defined by a post-treatment EPS score of 0 and/or an 85% reduction in CADESI-03 score, had significantly higher pretreatment serum 25(OH)D concentrations than dogs with a suboptimal response (P = 0.003 and P = 0.03, respectively). Serum 25(OH)D concentrations were also measured in a previously published cohort of atopic dogs that were treated with ciclosporin. This cohort of dogs was recruited in a similar time frame to the prednisolone-treated dogs, and all samples were handled in the same way. In contrast to the prednisolone-treated dogs, there was no significant difference in 25(OH)D concentrations in dogs that responded optimally to ciclosporin compared with suboptimal responders. Additional studies are required to establish whether vitamin D has a synergistic therapeutic effect with prednisolone in dogs with atopic dermatitis.     

Stomatal response of an anisohydric grapevine cultivar to evaporative demand, available soil moisture and abscisic acid

Stomatal responsiveness to evaporative demand (air vapour pressure deficit (VPD)) ranges widely between species and cultivars, and mechanisms for stomatal control in response to VPD remain obscure. The interaction of irrigation and soil moisture with VPD on stomatal conductance is particularly difficult to predict, but nevertheless is critical to instantaneous transpiration and vulnerability to desiccation. Stomatal sensitivity to VPD and soil moisture was investigated in Semillon, an anisohydric Vitis vinifera L. variety whose leaf water potential (Ψ(l)) is frequently lower than that of other grapevine varieties grown under similar conditions in the warm grape-growing regions of Australia. A survey of Semillon vines across seven vineyards revealed that, regardless of irrigation treatment, midday Ψ(l) was dependent on not only soil moisture but VPD at the time of measurement. Predawn Ψ(l) was more closely correlated to not only soil moisture in dry vineyards but to night-time VPD in drip-irrigated vineyards, with incomplete rehydration during high night-time VPD. Daytime stomatal conductance was low only under severe plant water deficits, induced by extremes in dry soil. Stomatal response to VPD was inconsistent across irrigation regime; however, in an unirrigated vineyard, stomatal sensitivity to VPD-the magnitude of stomatal response to VPD-was heightened under dry soils. It was also found that stomatal sensitivity was proportional to the magnitude of stomatal conductance at a reference VPD of 1kPa. Exogenous abscisic acid (ABA) applied to roots of Semillon vines growing in a hydroponic system induced stomatal closure and, in field vines, petiole xylem sap ABA concentrations rose throughout the morning and were higher in vines with low Ψ(l). These data indicate that despite high stomatal conductance of this anisohydric variety when grown in medium to high soil moisture, increased concentrations of ABA as a result of very limited soil moisture may augment stomatal responsiveness to low VPD.     

Characterization of the origin and body of the normal equine rear suspensory ligament using ultrasonography, magnetic resonance imaging, and histology

The suspensory ligament is difficult to image accurately, partly because it contains ligamentous fibers, as well as noncollagenous adipose and muscle tissue in the normal horse. Our hypothesis was that magnetic resonance (MR) imaging would be more accurate than ultrasonography in identifying the size of the suspensory ligament and the presence and size of noncollagenous tissues within the ligament. Eleven horses were used for ultrasonographic and MR imaging and histologic evaluation of the rear suspensory ligament. The origin and body of the normal suspensory ligament had a heterogenous appearance on MR images with two separate islands of mixed signal intensity evident throughout its otherwise hypointense cross-sectional area. Histologically, there were isolated islands of muscle, adipose, loose connective tissue and dense collagenous partitions, organized in two separate bundles that extended through the full length of the suspensory ligament origin and body to the level of its bifurcation. Comparison of MR images with corresponding histologic sections confirmed that islands of heterogenous signal intensity in normal suspensory ligaments correlated well with these bundles. Using ultrasonography, it was impossible to distinguish these islands from surrounding dense collagenous tissue consistently. MR imaging determined the cross-sectional area of the suspensory ligament more accurately than ultrasonography. Based upon these results, MR imaging is superior to ultrasonography for assessment of the suspensory ligament. The appearance associated with normal ligament anatomy needs to be understood before MR signal variation can be considered as indicative of disease in the suspensory ligament.     

Prednisolone is associated with an increase in serum insulin but not serum fructosamine concentrations in dogs with atopic dermatitis

The aim of this study was to assess the effects of a standard therapeutic protocol of prednisolone (Pred) on glucose homeostasis in atopic dogs and compare it with previously published data for ciclosporin A (CsA). The central aim of the study was to assess and compare the effects of standard therapeutic protocols of prednisolone (Pred) and ciclosporin A (CsA) on glucose homeostasis in dogs with atopic dermatitis (CAD). Both treatments significantly reduced the physical signs of CAD, as determined by the canine atopic dermatitis extent and severity index version 3 (CADESI-03) and the Edinburgh Pruritus Scale (EPS). Post-treatment plasma glucose concentrations were not significantly different in the two groups, but serum insulin concentrations were significantly higher following Pred therapy (P<0.05). Serum fructosamine concentrations were not significantly different pre- and post-treatment with Pred, although previous studies had shown that CsA treatment increased fructosamine concentrations (P<0.005). The two treatment groups were recruited in a similar timeframe, were numerically matched and there were no differences in CADESI-03 and EPS scores between the CsA and Pred groups either before or after treatment. Thus, both CsA and Pred treatment were associated with mild disturbances in glucose metabolism, but only CsA therapy resulted in a significant increase in fructosamine concentrations. This information may be relevant to clinicians when considering therapeutic options for dogs with atopic dermatitis which already have impaired glucose homeostasis.     

Does Shrub Removal Increase Groundwater Recharge in Southwestern Texas Semiarid Rangelands?

Evapotranspiration (ET) is a key component limiting groundwater recharge past the root zone in semiarid regions. Vegetation management may alter groundwater recharge if ET is altered due to changes in vegetation type or cover. This study quantifies changes in groundwater recharge following vegetation cover change from native woodland to pasture in a semiarid region of southwest Texas. The Carrizo–Wilcox aquifer is a valuable groundwater resource in this area, where overuse by dependent farming practices has lowered aquifer levels significantly in the last 85 yr. Combining data from short-term (30 mo) monitoring of the changes in soil moisture and long-term (5–30 yr) changes in total soil chloride indicated deep drainage increased slightly where land had been cleared of vegetation. Annual recharge rates below rooting depths (standardized to 155 cm) averaged only 0.72 ±  mm · yr^-1 (mean ± SE) in areas not cleared of woody vegetation, as estimated by chloride mass balance. Upon clearing, 72% of the total chloride naturally occurring in the soil profile was flushed away within 30 yr, leading to an estimated 2.59 ±  mm · yr^-1 additional recharge. Deep soil moisture in recently cleared land increased by up to 17% during the growing season of wet years (double the average rainfall) but did not increase in dry or normal precipitation years, providing supporting evidence that more water penetrated below the roots under certain environmental conditions. These results demonstrate that brush management can increase recharge by modest, but measurable, amounts depending on site-specific soil characteristics and degree of reduction in vegetation.