Allylic C-H functionalization via group 9 π-allyl intermediates.

Allylic C-H functionalization catalysed by group 9 Cp* transition-metal complexes has recently gained significant attention. These reactions have expanded allylic C-H functionalization to include di- and trisubstituted olefins, and a broad range of coupling partners. More specifically, several catalytic C-N, C-O, and C-C bond forming allylic C-H functionalization reactions have been reported, proceeding via MCp*-π-allyl intermediates. Herein we present an overview of these reactions by mechanistic paradigm. We also place this information in context of recent advances, as well as, limitations that remain for this class of reactions.

The Mechanism of Rhodium-Catalyzed Allylic C-H Amination.

Herein, the mechanism of catalytic allylic C-H amination reactions promoted by Cp*Rh complexes is reported. Reaction kinetics experiments, stoichiometric studies, and DFT calculations demonstrate that the allylic C-H activation to generate a Cp*Rh(π-allyl) complex is viable under mild reaction conditions. The role of external oxidants in the catalytic cycle is elucidated. Quantum mechanical calculations, stoichiometric reactions, and cyclic voltammetry experiments concomitantly support an oxidatively induced reductive elimination process of the allyl fragment with an acetate ligand proceeding through a Rh(IV) intermediate. Stoichiometric oxidation and bulk electrolysis of the proposed π-allyl intermediate are also reported to support these analyses. Lastly, evidence supporting the amination of an allylic acetate intermediate is presented. We show that Cp*Rh(III)2+ behaves as a Lewis acid catalyst to complete the allylic amination reaction.

Regioselective Cp*Ir(III)-Catalyzed Allylic C-H Sulfamidation of Allylbenzene Derivatives.

In this study we report the development of the regioselective Cp*Ir(III)-catalyzed allylic C-H sulfamidation of allylbenzene derivatives, using azides as the nitrogen source. The reaction putatively proceeds through a Cp*Ir(III)-π-allyl intermediate and demonstrates exclusive regioselectivity for the branched position of the π-allyl. The reaction performs well on electron-rich and electron-deficient allylbenzene derivatives and is tolerant of a wide range of functional groups, including carbamates, esters, and ketones. The proposed mechanism for this reaction proceeds via C-N reductive elimination from a Cp*Ir(V) nitrenoid complex at the branched position of the π-allyl.

OakEcol: A database of Oak-associated biodiversity within the UK.

Globally there is increasing concern about the decline in the health of oak Quercus trees. The impact of a decline in oak trees on associated biodiversity, species that utilize oak trees, is unknown. Here we collate a database of all known birds, bryophytes, fungi, invertebrates, lichens and mammals that use oak (Quercus petraea and Q. robur) in the UK. In total 2300 species are listed in the database. For each species we provide a level of association with oak, ranging from obligate (only found on oak) to cosmopolitan (found on a wide range of other tree species). Data on the ecology of each oak associated species was collated: part of tree used, use made of tree (feeding, roosting, breeding), age of tree, woodland type, tree form (coppice, pollarded, or natural growth form) and season when the tree was used. Data on use or otherwise by each of the 2300 species of 30 other tree species was also collated. A complete list of data sources is provided. For further insights into how this data can be used see Collapsing foundations: The ecology of the British oak, implications of its decline and mitigation options [1]. Data can be found at EIDC https://doi.org/10.5285/22b3d41e-7c35-4c51-9e55-0f47bb845202.

Intermolecular Allylic C-H Etherification of Internal Olefins.

Herein we report on the development of an oxidative allylic C-H etherification reaction, utilizing internal olefins and alcohols as simple precursors. Key advances include the use of RhCp* complexes to promote the allylic C-H functionalization of internal olefins and the compatibility of the oxidative conditions with oxidatively sensitive alcohols, enabling the direct etherification reaction. Preliminary mechanistic studies, consistent with C-H functionalization as the rate determining step, are presented.

Helical Turing patterns in the Lengyel-Epstein model in thin cylindrical layers.

The formation of Turing patterns was investigated in thin cylindrical layers using the Lengyel-Epstein model of the chlorine dioxide-iodine-malonic acid reaction. The influence of the width of the layer W and the diameter D of the inner cylinder on the pattern with intrinsic wavelength l were determined in simulations with initial random noise perturbations to the uniform state for W < l/2 and D ∼ l or lower. We show that the geometric constraints of the reaction domain may result in the formation of helical Turing patterns with parameters that give stripes (b = 0.2) or spots (b = 0.37) in two dimensions. For b = 0.2, the helices were composed of lamellae and defects were likely as the diameter of the cylinder increased. With b = 0.37, the helices consisted of semi-cylinders and the orientation of stripes on the outer surface (and hence winding number) increased with increasing diameter until a new stripe appeared.

A bistable switch in pH in urease-loaded alginate beads.

A bistable switch from a low pH (unreacted "off") state to a high pH (reacted "on") state was obtained in enzyme-loaded gel beads in response to supra-threshold substrate concentrations.

Regional scale gradients of climate and nitrogen deposition drive variation in ectomycorrhizal fungal communities associated with native Scots pine.

Ectomycorrhizal fungi commonly associate with the roots of forest trees where they enhance nutrient and water uptake, promote seedling establishment and have an important role in forest nutrient cycling. Predicting the response of ectomycorrhizal fungi to environmental change is an important step to maintaining forest productivity in the future. These predictions are currently limited by an incomplete understanding of the relative significance of environmental drivers in determining the community composition of ectomycorrhizal (ECM) fungi at large spatial scales. To identify patterns of community composition in ECM fungi along regional scale gradients of climate and nitrogen deposition in Scotland, fungal communities were analysed from 15 seminatural Scots pine (Pinus sylvestris L.) forests. Fungal taxa were identified by sequencing of the ITS rDNA region using fungal-specific primers. Nonmetric multidimensional scaling was used to assess the significance of 16 climatic, pollutant and edaphic variables on community composition. Vector fitting showed that there was a strong influence of rainfall and soil moisture on community composition at the species level, and a smaller impact of temperature on the abundance of ectomycorrhizal exploration types. Nitrogen deposition was also found to be important in determining community composition, but only when the forest experiencing the highest deposition (9.8 kg N ha(-1)  yr(-1) ) was included in the analysis. This finding supports previously published critical load estimates for ectomycorrhizal fungi of 5-10 kg N ha(-1)  yr(-1) . This work demonstrates that both climate and nitrogen deposition can drive gradients of fungal community composition at a regional scale.

Genetic host-tree effects on the ectomycorrhizal community and root characteristics of Norway spruce.

A greenhouse experiment was used to study the effects of host genotype on short root formation and ectomycorrhizal (ECM) fungal community structure in Norway spruce (Picea abies (L.) Karst.). Rooted cuttings representing 55 clones were inoculated with a mix of vegetative hyphae of five ECM fungal species (Laccaria sp., Amphinema byssoides, Piloderma sp., Cadophora finlandia, Paxillus involutus). After one growing season, the ECM fungal community structure was determined by amplifying the fungal internal transcribed spacer (ITS) of ribosomal DNA directly from ECM root tips. Restriction profiles of obtained amplicons were then compared to those of the inoculated strains. Spruce clones differed in their ECM fungal community composition; we found a statistically significant clone-specific effect on ECM fungal diversity and dominating fungal species. Nevertheless, the broad sense heritabilities of the levels of Laccaria sp., Piloderma sp. and A. byssoides colonisations as well as the ECM fungal community structure were low (H(2) = 0.04-0.11), owing to the high within-clone variation. As nitrogen concentration of needles correlated negatively with ECM fungal richness, our results imply that in the experimental conditions nutrient acquisition of young trees may benefit from colonisation with only one or two ECM fungal species. The heritability of short root density was moderate (H(2) = 0.41) and highest among all the measured shoot and root growth characteristics of Norway spruce cuttings. We suggest that the genetic component determining root growth and short root formation is significant for the performance of young trees in natural environments as these traits drive the formation of the below-ground symbiotic interactions.

Complex organizing centers in groups of oscillatory particles.

We investigate the origin and evolution of spatiotemporal complexity in a system of locally coupled Belousov-Zhabotinsky chemical oscillators. Using a combination of high resolution microscopy and fine grain numerical modeling, we demonstrate that the behavior arises from an initial phase heterogeneity of the oscillators. This heterogeneity produces wave breaks in the system with the free ends becoming pinned to holes in the medium. The fastest of these pinned tips behave as reentrant circuits that phase set the rest of the medium. The slower tips are repeatedly destroyed and then re-created by the central circuit. The resulting spatiotemporal pattern repeats with the frequency of the reentrant circuit, with its spatial structure depending on the location of the initial wave breaks.

Accumulation of potassium, rubidium and caesium (133Cs and 137Cs in various fractions of soil and fungi in a Swedish forest.

Radiocaesium ((137)Cs) was widely deposited over large areas of forest in Sweden as a result of the Chernobyl accident in 1986 and many people in Sweden eat wild fungi and game obtained from these contaminated forests. In terms of radioisotope accumulation in the food chain, it is well known that fungal sporocarps efficiently accumulate radiocaesium ((137)Cs), as well as the alkali metals potassium (K), rubidium (Rb) and caesium (Cs). The fungi then enhance uptake of these elements into host plants. This study compared the accumulation of these three alkali metals in bulk soil, rhizosphere, soil-root interface, fungal mycelium and sporocarps of mycorrhizal fungi in a Swedish forest. The soil-root interface was found to be distinctly enriched in K and Rb compared with the bulk soil. Potassium concentrations increased in the order: bulk soil

Relative efficiency of chlamydia screening in non-clinical settings in two California counties.

We examined the relative efficiency of non-clinical sites to screen for chlamydia in youth and young adults. Chlamydia screening targeting youth (under 30 years of age) was performed at non-clinical sites in high-morbidity neighbourhoods of two California counties. Venues were subdivided into community outreach, schools, parenting centres and drug treatment/correctional facilities. Relative efficiency was estimated with multivariate Poisson regression using incidence of chlamydia per person-hours labour adjusting for strategy and county. Among the 1514 youths screened, the overall prevalence of chlamydia was 5.5%. By venue, the highest prevalence was in drug treatment/correction facilities at 11.1% followed by parenting centres at 6.3%, community outreach at 4.9% and schools at 4.6%. Drug treatment/correctional facilities were the most labour time efficient at 9.9 person-hours per chlamydia case. Schools and parenting centres had the lowest cost per screen at 0.9 person-hours per screen. Adjusted relative labour time efficiency (chlamydia cases per paid person-hour) was significantly higher in schools, 2.0 (95% confidence interval [CI] 1.0-4.2), parenting centres, 3.2 (95% CI 1.6-6.6) and drug treatment/correctional facilities, 2.9 (95% CI 1.0-7.8), compared with community outreach. In conclusion, parenting centres and drug treatment centres and correctional facilities are the most efficient venues for chlamydia screening.

Afforestation of abandoned farmland with conifer seedlings inoculated with three ectomycorrhizal fungi - impact on plant performance and ectomycorrhizal community.

The aim of a 3-year study was to investigate whether inoculation of Pinus sylvestris L. and Picea abies (L.) Karst. seedlings with mycorrhizas of Cenococcum geophilum Fr., Piceirhiza bicolorata, and Hebeloma crustuliniforme (Bull.) Quel. has any impact on: 1) survival and growth of outplanted seedlings on abandoned agricultural land, and 2) subsequent mycorrhizal community development. For inoculation, the root system of each plant was wrapped in a filter paper containing mycelium, overlaid with damp peat-sand mixture and wrapped in a paper towel. In total, 8,000 pine and 8,000 spruce seedlings were planted on 4-ha of poor sandy soil in randomized blocks. Already after the first year natural mycorrhizal infections prevailed in the inoculated root systems, and introduced mycorrhizas were seldom found. Yet, the seedlings that had been pre-inoculated with C. geophilum and the P. bicolorata during the whole 3-year period showed significantly higher survival and growth as compared to controls. Moreover, the independent colonization of roots by C. geophilum and the P. bicolorata from natural sources was also observed. A diverse mycorrhizal community was detected over two growing seasons in all treatments, showing low impact of inoculation on subsequent fungal community development. A total of 19 additional ectomycorrhizal morphotypes was observed, which clustered into two well-separated groups, according to host tree species (pine and spruce). In conclusion, the results showed limited ability to increase tree survival and growth, and to manipulate the mycorrhizal community even by extensive pre-inoculations, indicating that fungal community formation in root systems is governed mainly by environmental factors.

Mechanically stimulated osteocytes regulate osteoblastic activity via gap junctions.

The strong correlation between a bone's architectural properties and the mechanical forces that it experiences has long been attributed to the existence of a cell that not only detects mechanical load but also structurally adapts the bone matrix to counter it. One of the most likely cellular candidates for such a "mechanostat" is the osteocyte, which resides within the mineralized bone matrix and is perfectly situated to detect mechanically induced signals. However, as osteocytes can neither form nor resorb bone, it has been hypothesized that they orchestrate mechanically induced bone remodeling by coordinating the actions of cells residing on the bone surface, such as osteoblasts. To investigate this hypothesis, we developed a novel osteocyte-osteoblast coculture model that mimics in vivo systems by permitting us to expose osteocytes to physiological levels of fluid shear while shielding osteoblasts from it. Our results show that osteocytes exposed to a fluid shear rate of 4.4 dyn/cm(2) rapidly increase the alkaline phosphatase activity of the shielded osteoblasts and that osteocytic-osteoblastic physical contact is a prerequisite. Furthermore, both functional gap junctional intercellular communication and the mitogen-activated protein kinase, extracellular signal-regulated kinase 1/2 signaling pathway are essential components in the osteoblastic response to osteocyte communicated mechanical signals. By utilizing other nonosteocytic coculture models, we also show that the ability to mediate osteoblastic alkaline phosphatase levels in response to the application of fluid shear is a phenomena unique to osteocytes and is not reproduced by other mesenchymal cell types.

Mechanical stimulation effects on functional end effectors in osteoblastic MG-63 cells.

Receptor activator of Nf-kappaB ligand (RANKL) and osteoprotegerin (OPG) have been implicated in bone metabolism. Specifically, the balance of these factors in conjunction with receptor activator of Nf-kappaB (RANK) is believed to be key in determining the rate of osteoclastogenesis and the net outcome of bone formation/resorption. While it is well accepted that mechanical loading in vivo affects bone formation/resorption and that alterations in the responsiveness of bone cells to mechanical loading have been implicated in metabolic bone diseases, the effect of in vitro mechanical loading on osteoblastic production of OPG and RANKL has not been extensively studied. Thus, in the current study, we developed an in vitro model to load human osteoblasts and studied levels of OPG, RANKL, PGE(2) and macrophage colony stimulating factor (M-CSF). We hypothesized that stimulating osteoblastic cells would increase the release of soluble OPG relative to RANKL favoring a bone-forming (and resorption-inhibiting) event. To accomplish this, we developed a small-scale loading machine that imparts via bending, well-defined substrate deformation to bone cells cultured on artificial substrates. Following 2h of loading and a 1h incubation period, media was collected and levels of soluble OPG, RANKL, PGE(2) and M-CSF were quantified using ELISA and western blotting. We found that mechanical loading significantly increased soluble OPG levels relative to RANKL at this 3h time point. Levels of soluble and cellular RANKL detected were not significantly affected by mechanical stimulation. The relative shift in abundance of OPG over RANKL associated with applied mechanical stimulation suggests the soluble OPG:RANKL ratio may be important in load-induced coupling mechanisms of bone cells.

Complex behavior in the formaldehyde-sulfite reaction.

The formaldehyde-sulfite reaction is an example of an "acid-to-alkali" clock. It displays an induction period, during which the pH varies only slowly in time, followed by a reaction event, during which the pH increases rapidly by several units. When the reaction is performed in a closed (batch) reactor, the clock time is found to increase with a decrease in initial concentrations of formaldehyde and sulfite and an increase in the total initial concentration of S(IV). At long times, following the clock event, there is a slow decrease in pH. In an open (flow) reactor, bistability between a low-pH steady state (pH approximately 6-8) and a high-pH steady state (pH approximately 11) is observed. Additionally, we report the existence of sustained, small-amplitude oscillations in pH in this system. An extended kinetic mechanism reproduces the batch behavior but fails to account for the complex behavior observed in the flow reactor. Possible additional reaction steps are discussed.

Uptake of nitrogen and carbon from double-labelled (15 N and 13 C) glycine by mycorrhizal pine seedlings.

• While it is accepted that many ectomycorrhizal fungi can assimilate organic substrates and facilitate transfer of their elemental components to plants, the fate of the carbon contained in these materials remains uncertain. Here we investigate the compartmentation of carbon and nitrogen in ectomycorrhizal seedlings of Pinus sylvestris fed with double-labelled (15 N and 13 C) glycine as their sole N source. • Using isotope ratio mass spectrometry, the quantities of N and C derived from this glycine were determined in sequentially harvested samples of mycorrhizas, roots and shoots. • Whereas considerable quantities of 15 N were observed in the mycorrhizal tips, roots and shoots, comparable amounts of 13 C were observed only in mycorrhizal tips and roots. • It is clearly important to resolve the role of compound specificity as a factor determining the extent of amino-acid C transfer from roots to shoots. However, from the standpoint of the C budget of the whole plant, wherever heterotrophically acquired C is available as an energy source it will reduce demands on photosynthetically fixed sources of the element.

Vertical distribution of ectomycorrhizal fungal taxa in a podzol soil profile.

• Studies of ectomycorrhizal fungal communities in forest soils are usually restricted to the uppermost organic horizons. Boreal forest podzols are highly stratified and little is known about the vertical distribution of ectomycorrhizal communities in the underlying mineral horizons. • Ectomycorrhizal root tips were sampled from seven horizons in three continuous columns of a 52-cm deep podzol profile. Root tips were sorted into morphological groups and the colonising fungi identified by sequencing of the rDNA ITS region. The vertical distribution of mycorrhizal taxa was examined. • A relationship between ectomycorrhizal species composition and soil horizon was found. Tomentellopsis submollis, three Piloderma species and Dermocybe spp. were found predominantly in the upper horizons while Suillus luteus, Lactarius utilis and three undescribed Piloderma species were associated with the mineral horizons. • Two thirds of the root tips were found in the mineral soil and half of the taxa were restricted to the mineral horizons. The results highlight the need to include the mineral soil in order to gain a more accurate representation of the ectomycorrhizal community.

Functional osteoblastic ionotropic glutamate receptors are a prerequisite for bone formation.

Many studies have now demonstrated that osteoblasts express the protein components necessary for functional neuronal-like glutamatergic signalling to occur, and as a result a physiological role for receptor mediated osteoblastic glutamate signalling has been proposed. Osteoblastic ionotropic type glutamate receptors (iGluRs) have been shown to be functional; they possess electrophysiological characteristics similar to neuronal iGluR) and agonist application modulates the activity of intracellular signalling molecules and osteoblastic transcription factors. The physiological importance of osteoblastic iGluRs is illustrated by the fact that osteoblasts treated in vitro with non-competitive iGluR antagonists fail to form mineralized bone. Interestingly compounds known to antagonize specific sub-types of iGluR induce different effects when applied to osteoblasts derived from long and flat bones. These data imply that not only are functional osteoblastic iGluRs a prerequisite for osteoblast differentiation and bone formation, but also that the components of osteoblastic glutamatergic signalling may be adapted to reflect the differential function of osteoblasts from different skeletal sites. This paper reviews the evidence that suggests that iGluR-mediated glutamate signalling plays a fundamental role in the regulation of osteoblast function and bone formation, and discusses the therapeutic potential of manipulation of osteoblastic iGluR to modulate bone homeostasis.