What is the initiation step of the Grubbs-Hoveyda olefin metathesis catalyst?

Density function theory calculations reveal that the Grubbs-Hoveyda olefin metathesis pre-catalyst is activated by the formation of a complex in which the incoming alkene substrate and outgoing alkoxy ligand are both clearly associated with the ruthenium centre. The computed energies for reaction are in good agreement with the experimental values, reported here

Solvent effects on Grubbs’ pre-catalyst initiation rates

Initiation rates for Grubbs and Grubbs-Hoveyda second generation pre-catalysts have been measured accurately in a range of solvents. Solvatochromic fitting reveals different dependencies on key solvent parameters for the two pre-catalysts, consistent with different mechanisms by which the Grubbs and Grubbs-Hoveyda pre-catalysts initiate

Increasing Skin Infections and Staphylococcus aureus Complications in Children, England, 1997-2006

During 1997-2006, general practitioner consultations for skin conditions for children <18 years of age in England increased 19%, from 128.5 to 152.9/1,000 child-years, and antistaphylococcal drug prescription rates increased 64%, from 17.8 to 29.1/1,000 child-years. During the same time period, hospital admissions for Staphylococcus aureus infections rose 49% from 53.4 to 79.3/100,000 child-years.link_to_subscribed_fulltex

Exogenous monoterpenes mitigate H2O2-induced lipid damage but do not attenuate photosynthetic decline during water deficit in tomato

Although monoterpenes are suggested to mediate oxidative status, their role in abiotic stress responses is currently unclear. Here, a foliar spray of monoterpenes increased antioxidant capacity and decreased oxidative stress of Solanum lycopersicum under water deficit stress. The foliar content of monoterpenes increased with spray concentration indicating foliar uptake of exogenous monoterpenes. Exogenous monoterpene application substantially decreased foliar accumulation of hydrogen peroxide (H2O2) and lipid peroxidation (malondialdehyde). However, it appears that monoterpenes prevent the accumulation of reactive oxygen species rather than mitigating subsequent reactive oxygen species-induced damage. Low spray concentration (1.25 mM) proved most effective in decreasing oxidative stress but did not up-regulate the activity of key antioxidant enzymes (superoxide dismutase and ascorbate peroxidase) even though higher (2.5 and 5 mM) spray concentrations did, suggesting a complex role for monoterpenes in mediating antioxidant processes. Furthermore, soil drying caused similar photosynthetic limitations in all plants irrespective of monoterpene treatments, apparently driven by strong reductions in stomatal conductance as photosystem II efficiency only decreased in very dry soil. We suggest that exogenous monoterpenes may mitigate drought-induced oxidative stress by direct quenching and/or up-regulating endogenous antioxidative processes. The protective properties of specific monoterpenes and endogenous antioxidants require further investigation

Chronic tropospheric ozone exposure reduces seed yield and quality in spring and winter oilseed rape

Oilseed rape (Brassica napus L.) is cultivated worldwide, producing 11.5% of global oilseeds at an economic value of 38 billion USD in 2020. It is sensitive to phytotoxic damage from exposure to tropospheric ozone (O3), a major air pollutant, which disrupts plant physiological processes and thus decreases biomass accumulation. As background ozone concentrations continue to increase globally, we investigated the impact of ozone exposure on seed and oil yield of a shorter-lived spring (cv. Click) and a longer-lived winter (cv. Phoenix) oilseed rape cultivar to ozone levels (treatments with peaks of 30, 55, 80, 110 ppbv) representative of typical European conditions where these cultivars are common. Thousand Seed Weight (TSW), an important measure of final yield, decreased more in Phoenix (40%) than Click (20%) with increasing ozone exposure. Click produced more racemes and many small seeds while Phoenix produced fewer racemes and larger seeds. However, seed quality declined more substantially in Click than Phoenix. The oil content in Click's seed significantly decreased with increased ozone exposure, while less desirable components (moisture, chlorophyll, ash) increased. Scaled to field-level, our findings imply substantial economic penalties for growers, with potential losses of 175–325 USD ha−1 in Click and 500–665 USD ha−1 in Phoenix under ozone concentrations typical of spring and summer periods in Europe. Decreased total yield would likely outweigh the benefits of any improvement in animal oilseed cake quality (increased protein and key micronutrients for livestock feed). Neither cultivar sustained visible injury at earlier growth stages, and Phoenix sustained photosynthesis even under high exposure, thereby making ozone an invisible threat. Our findings of reduced oilseed quantity and quality threaten oilseed rape production, but differences between the cultivars may also offer an opportunity for breeders and agronomists to identify and exploit variation in ozone tolerance in oilseed rape

How Will Changing Climate Conditions Affect Volatile Organic Compounds in Temperate Forests?

The rise in atmospheric CO2 has far-reaching consequences for terrestrial ecosystems, particularly forests. This impact stems from direct CO2 effects, changes in precipitation patterns, and an increased likelihood of drought and heat waves. Forests, major contributors of biogenic volatile organic compounds (BVOCs), play a crucial role in this interaction. Among BVOCs, isoprene (C5H8) is the most abundant in temperate and tropical forests, with high reactivity in the atmosphere, leading to various oxidation products. Other BVOCs in lower quantities in temperate forests exhibit significant photochemical and ecological activity emanating from foliage and the forest floor. This doctoral thesis aims to unravel the impact of elevated CO2 on VOC emissions from a temperate forest. It focuses on isoprene emissions and concentrations from the canopy and BVOC concentrations from the soil. The study explores the short-term effects of drought and high-temperature events on isoprene emissions. It investigates the potential long-term "legacy" effects of drought on isoprene seasonality through changes in leaf phenology. The research, utilising Birmingham's BIFoR FACE facility, represents the first effort to collect isoprene data under long-term CO2 fumigation in a mature forest. Findings reveal decreased leaf-level emissions and canopy concentrations under elevated CO2, aligning with previous laboratory data. Conducting a pioneering field experiment at BIFoR FACE, the study explores the impact of elevated CO2 on soil VOCs. Results indicate a consistent decrease in soil chamber concentrations under elevated CO2, mirroring the canopy trend. Additional experiments on root exudates and leaf litter offer insights into key drivers influencing the decline in soil VOCs. The final study uses isoprene observations over four growing seasons to model isoprene response to drought and heat waves. It highlights the need for models to consider extreme heat and soil moisture effects. Examining Wytham Woods, the study finds no change in isoprene seasonality in 2019 following the 2018 moderate drought, suggesting no discernible long-term legacy effects of drought on emissions. These insights contribute to understanding the nuanced responses of isoprene emissions to environmental stressors

Toward a simulation approach for alkene ring-closing metathesis : scope and limitations of a model for RCM

A published model for revealing solvent effects on the ring-closing metathesis (RCM) reaction of di-Et diallylmalonate 7 has been evaluated over a wider range of conditions, to assess its suitability for new applications. Unfortunately, the model is too flexible and the published rate consts. do not agree with exptl. studies in the literature. However, by fixing the values of important rate consts. and restricting the concn. ranges studied, useful conclusions can be drawn about the relative rates of RCM of different substrates, precatalyst concn. can be simulated accurately and the effect of precatalyst loading can be anticipated. Progress has also been made toward applying the model to precatalyst evaluation, but further modifications to the model are necessary to achieve much broader aims

Micro-CT Imaging of Pediatric Thyroglossal Duct Cysts: A Prospective Case Series

Objectives: To determine the feasibility of micro-CT as a high-resolution 3D imaging tool for thyroglossal duct cysts and to evaluate its role augmenting traditional histopathological examination of resected specimens. Methods: A single centre, prospective case series of consecutive children undergoing excision of a thyroglossal duct cyst was performed at a quaternary paediatric referral hospital in the United Kingdom. Consecutive children listed for excision of a thyroglossal duct cyst whose parents agreed to participate were included and there were no exclusion criteria. Results: Surgically excised thyroglossal duct cyst or remnant specimens from five patients (two males, three females) were examined using micro-CT alongside traditional histopathological examination. In all cases, micro-CT imaging was able to demonstrate 3D imaging datasets of the specimens successfully and direct radio-pathological comparisons were made (Figures 1–5, Supplementary Video 1). Conclusions: The study has shown the feasibility and utility of post-operative micro-CT imaging of thyroglossal duct cysts specimens as a visual aid to traditional histopathological examination. It better informs the pathological specimen sectioning using multi-planar reconstruction and volume rendering tools without tissue destruction. In the complex, often arborised relationship between a thyroglossal duct cyst and the hyoid, micro-CT provides valuable image plane orientation and indicates proximity of the duct to the surgical margins. This is the first case series to explore the use of micro-CT imaging for pediatric thyroglossal duct specimens and it informs future work investigating the generalizability of micro-CT imaging methods for other lesions, particularly those from the head and neck region where precisely defining margins of excision may be challenging

Toroidal Compactification in String Theory from Chern-Simons Theory

A detailed study of the charge spectrum of three dimensional Abelian Topological Massive Gauge Theory (TMGT) is given. When this theory is defined on a manifold with two disconnected boundaries there are induced chiral Conformal Field Theories (CFT's) on the boundaries which can be interpreted as the left and right sectors of closed strings. We show that Narain constraints on toroidal compactification (integer, even, self-dual momentum lattice) have a natural interpretation in purely three dimensional terms. This is an important result which is necessary to construct toroidal compactification and heterotic string from Topological Membrane (TM) approach to string theory. We also derive the block structure of $c=1$ Rational Conformal Field Theory (RCFT) from the three dimensional gauge theory.Comment: 32+2 pages, 9 figures. Comments added and minor changes in section 3. Content not altere