958 research outputs found

    Diversity, functional structure and functional redundancy of woodland plant communities: How do mixed tree species plantations compare with monocultures?

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    Managing forest plantation stands in a way that retains productivity targets, but that also fosters biodiversity and stand resilience are key sustainable forest management goals. Current forestry policy advocates a diversification of forest stands to achieve these goals, favouring mixed age structures and polycultures over single-aged monocultures. Evidence is lacking, however, to support this management recommendation for biodiversity gains and related ecosystem service delivery. We used indices of taxonomic diversity and functional structure to compare ground vegetation communities in mixed and pure stands of Scots pine (Pinus sylvestris) and pedunculate oak (Quercus robur) in each of three study regions. We categorised the 91 vascular plant species identified into functional effect and response groups. We tested the hypotheses that ground vegetation communities (i) differ significantly in structure and composition between Scots pine and oak monocultures and (ii) show enhanced levels of taxonomic and functional diversity and functional redundancy in mixed stands of Scots pine and oak compared with monocultures. We explored the implications of any differences in the functional structure of ground vegetation communities in the different stand types on two ecosystem services: nutrient availability and levels of resource provisioning for herbivores. Nine functional response groups (RG) and seven functional effect groups (EG) were identified with considerable overlap in the RG and EG species grouping. Three RGs had traits characteristic of forests (spring flowering herbs, tree saplings and shrubs/ climbers), one RG had traits characteristic of open habitats (annual ruderals) and the remaining RGs had more generalist traits (anemochorous perennials, graminoids and short perennials). No significant differences were found among stand types in terms of taxonomic diversity or richness of the different functional trait groups. Ground vegetation communities in the three study regions also had similar levels of functional redundancy across stand types. However, Scots pine and oak monocultures harboured significantly different abundances of species with distinct functional traits. In all three study regions, anemochorous perennials were significantly more abundant in Scots pine monocultures than oak monocultures, while two core forest groups (shrubs/ climbers, spring flowering herbs) were significantly more abundant in oak monocultures. Mixed stands had intermediate abundances of these functional groups. These differences have implications for the comparative availability of food resources and shelter for wildlife, but also the mobilisation and temporal availability of nutrients in the two monocultures. Thus, mixtures of Scots pine and pedunculate oak can temper significant tree species identity influences on ground vegetation functional diversity

    New insight into the formation of structural defects in poly(vinyl chloride)

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    The monomer conversion dependence of the formation of the various types of defect structures in radical suspension polymerization of vinyl chloride was examined via both H-1 and C-13 NMR spectrometry. The rate coefficients for model propagation and intra- and intermolecular hydrogen abstraction reactions were obtained via high-level ab initio molecular orbital calculations. An enormous increase in the formation of both branched and internal unsaturated structures was observed at conversions above 85%, and this is mirrored by a sudden decrease in stability of the resulting PVC polymer. Above this threshold-conversion, the monomer is depleted from the polymer-rich phase, and the propagation rate is thus substantially reduced, thereby allowing the chain-transfer processes to compete more effectively. In contrast to the other defects, the chloroallylic end groups were found to decrease at high conversions. On the basis of the theoretical and experimental data obtained in this study, this decrease was attributed to copolymerization and abstraction reactions that are expected to be favored at high monomer conversions. Finally, a surprising increase in the concentration of the methyl branches was reported. Although a definitive explanation for this behavior is yet to be obtained, the involvement of transfer reactions of an intra- or intermolecular nature seems likely, and (in the latter case) these could lead to the presence of tertiary chlorine in these defects

    Carbapenem-only combination therapy against multi-drug resistant Pseudomonas aeruginosa : assessment of in vitro and in vivo efficacy and mode of action

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    Funding: This research was funded by the University of St Andrews.The aim of the study was to determine the efficacy of carbapenem-only combination treatments derived from four approved drugs (meropenem, doripenem, ertapenem and imipenem) against a MDR strain of P. aeruginosa in a Galleria mellonella larvae infection model. G. mellonella larvae were infected with P. aeruginosa NCTC 13437 (carrying the VIM 10 carbapenamase) and the efficacy of the six possible dual, four triple, and one quadruple carbapenem combination(s) were compared to their constituent monotherapies. Four of these combinations showed significantly enhanced survival compared to monotherapies and reduced the bacterial burden inside infected larvae but without complete elimination. Bacteria that survived combination therapy were slower growing, less virulent but with unchanged carbapenem MICs—observations that are consistent with a persister phenotype. In vitro time-kill assays confirmed that the combinations were bactericidal and confirmed that a low number of bacteria survived exposure. Mass spectrometry was used to quantify changes in the concentration of carbapenems in the presence of carbapenemase-carrying P. aeruginosa. The rate of degradation of individual carbapenems was altered, and often significantly reduced, when the drugs were in combinations compared with the drugs alone. These differences may account for the enhanced inhibitory effects of the combinations against carbapenem-resistant P. aeruginosa and are consistent with a ‘shielding’ hypothesis. In conclusion, carbapenem combinations show promise in combating MDR P. aeruginosa and are worthy of additional study and development.Publisher PDFPeer reviewe

    Side Reactions of Nitroxide-Mediated Polymerization: N−O versus O−C Cleavage of Alkoxyamines

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    Free energies for the homolysis of the NO−C and N−OC bonds were compared for a large number of alkoxyamines at 298 and 393 K, both in the gas phase and in toluene solution. On this basis, the scope of the N−OC homolysis side reaction in nitroxide-mediated polymerization was determined. It was found that the free energies of NO−C and N−OC homolysis are not correlated, with NO−C homolysis being more dependent upon the properties of the alkyl fragment and N−OC homolysis being more dependent upon the structure of the aminyl fragment. Acyclic alkoxyamines and those bearing the indoline functionality have lower free energies of N−OC homolysis than other cyclic alkoxyamines, with the five-membered pyrrolidine and isoindoline derivatives showing lower free energies than the six-membered piperidine derivatives. For most nitroxides, N−OC homolysis is normally favored above NO−C homolysis only when a heteroatom that is α to the NOC carbon center stabilizes the NO−C bond and/or the released alkyl radical is not sufficiently stabilized. As part of this work, accurate methods for the calculation of free energies for the homolysis of alkoxyamines were determined. Accurate thermodynamic parameters to within 4.5 kJ mol−1 of experimental values were found using an ONIOM approximation to G3(MP2)-RAD combined with PCM solvation energies at the B3-LYP/6-31G(d) level

    Experimental evidence for competitive N-O and O-C bond homolysis in gas-phase alkoxyamines

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    The extensive use of alkoxyamines in controlled radical polymerisation and polymer stabilisation is based on rapid cycling between the alkoxyamine (R1R2NO-R3) and a stable nitroxyl radical (R1R2NO‱) via homolysis of the labile O-C bond. Competing homolysis of the alkoxyamine N-O bond has been predicted to occur for some substituents leading to production of aminyl and alkoxyl radicals. This intrinsic competition between the O-C and N-O bond homolysis processes has to this point been difficult to probe experimentally. Herein we examine the effect of local molecular structure on the competition between N-O and O-C bond cleavage in the gas phase by variable energy tandem mass spectrometry in a triple quadrupole mass spectrometer. A suite of cyclic alkoxyamines with remote carboxylic acid moieties (HOOC-R1R2NO-R3) were synthesised and subjected to negative ion electrospray ionisation to yield [M − H]− anions where the charge is remote from the alkoxyamine moiety. Collision-induced dissociation of these anions yield product ions resulting, almost exclusively, from homolysis of O-C and/or N-O bonds. The relative efficacy of N-O and O-C bond homolysis was examined for alkoxyamines incorporating different R3 substituents by varying the potential difference applied to the collision cell, and comparing dissociation thresholds of each product ion channel. For most R3 substituents, product ions from homolysis of the O-C bond are observed and product ions resulting from cleavage of the N-O bond are minor or absent. A limited number of examples were encountered however, where N-O homolysis is a competitive dissociation pathway because the O-C bond is stabilised by adjacent heteroatom(s) (e.g. R3 = CH2F). The dissociation threshold energies were compared for different alkoxyamine substituents (R3) and the relative ordering of these experimentally determined energies is shown to correlate with the bond dissociation free energies, calculated by ab initio methods. Understanding the structure-dependent relationship between these rival processes will assist in the design and selection of alkoxyamine motifs that selectively promote the desirable O-C homolysis pathway

    Localization of Interaction using Fibre-Optic Shape Sensing in Soft-Robotic Surgery Tools

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    Minimally invasive surgery requires real-time tool tracking to guide the surgeon where depth perception and visual occlusion present navigational challenges. Although vision-based and external sensor-based tracking methods exist, fibre-optic sensing can overcome their limitations as they can be integrated directly into the device, are biocompatible, small, robust and geometrically versatile. In this paper, we integrate a fibre Bragg grating-based shape sensor into a soft robotic device. The soft robot is the pneumatically attachable flexible (PAF) rail designed to act as a soft interface between manipulation tools and intra-operative imaging devices. We demonstrate that the shape sensing fibre can detect the location of the tools paired with the PAF rail, by exploiting the change in curvature sensed by the fibre when a strain is applied to it. We then validate this with a series of grasping tasks and continuous US swipes, using the system to detect in real-time the location of the tools interacting with the PAF rail. The overall location-sensing accuracy of the system is 64.6%, with a margin of error between predicted location and actual location of 3.75 mm

    Molecule‐Induced Radical Formation (MIRF) Reactions—A Reappraisal

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    Radical chain reactions are commonly initiated through the thermal or photochemical activation of purpose‐built initiators, through photochemical activation of substrates, or through well‐designed redox processes. Where radicals come from in the absence of these initiation strategies is much less obvious and are often assumed to derive from unknown impurities. In this situation, molecule‐induced radical formation (MIRF) reactions should be considered as well‐defined alternative initiation modes. In the most general definition of MIRF reactions, two closed‐shell molecules react to give a radical pair or biradical. The exact nature of this transformation depends on the σ‐ or π‐bonds involved in the MIRF process, and this Minireview specifically focuses on reactions that transform two σ‐bonds into two radicals and a closed‐shell product molecule

    Commentary on “Can a Good Philosophical Contribution Be Made Just By Asking a Question?”

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    This paper explains some of the reasoning behind “Can a Good Philosophical Contribution Be Made Just by Asking a Question?,” a paper which consists solely in its title and which is published in the same issue of the journal as the present paper. The method for explaining that reasoning consists in making available a lightly edited version of a letter the authors sent to the editors when submitting the title-only paper. The editors permitted publication of that paper on the condition that the authors also separately publish a version of that letter; the present paper aims to fulfil that condition
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