470 research outputs found

    Synthesis, crystallographic characterization and homogeneous catalytic activity of novel unsymmetric porphyrins

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    Unsymmetric porphyrins, containing both pentafluorophenyl (PFP = A) and 3,4-dimethoxyphenyl (DMP = B) substituents at the meso positions, were prepared using Lindsey's methodology. The isomeric trans-A2B2 (P1) and cis-A2B2 (P2) porphyrins together with the tris(pentafluorophenyl)porphyrin A3B (P3) were isolated using chromatography. The porphyrins were characterized by UV-VIS, 1H NMR spectroscopy, mass spectrometry, elemental analysis (C, H, N) and cyclic voltammetry (CV), and their molecular structures were confirmed by single crystal XRD. Their manganese complexes, MnP1, MnP2 and MnP3, were also synthesised and used as catalysts in cyclooctene and cyclohexane oxidation reactions under homogeneous conditions. The catalytic studies were supported by electrochemical measurements and showed that the number of electron-withdrawing substituents on the porphyrins rings influences the catalytic activity. These porphyrins may be used as precursors for the design of new materials, such as Polymers of Intrinsic Microporosity (PIMs)

    Quantum flavor oscillations extended to the Dirac theory

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    This report deals with the quantum theory of flavor oscillations in vacuum, extended to fermionic particles in the several subtle aspects of the first and second quantization theories. In this scenario, the use of the Dirac equation is required for a satisfactory evolution of fermionic mass-eigenstates since in the standard treatment of oscillations the mass-eigenstates are implicitly assumed to be scalars and, consequently, the spinorial form of neutrino wave functions is not included in the calculations. Within first quantized theories, besides flavor oscillations, chiral oscillations automatically appear when we set the dynamic equations for a fermionic Dirac-type particle. The left-handed chiral nature of created and detected neutrinos can be implemented in the first quantized Dirac theory in presence of mixing; the probability loss due to the changing of initially left-handed neutrinos to the undetected right-handed neutrinos can be obtained in analytic form. In the context of a causal relativistic theory of a free particle, one of the two effects should be present in flavor oscillations: (a) rapid oscillations or (b) initial flavor violation. Concerning second quantized approaches, a simple second quantized treatment exhibits a tiny but inevitable initial flavor violation without the possibility of rapid oscillations. Such effect is a consequence of an intrinsically indefinite but approximately well defined neutrino flavor. The violation effects are shown to be much larger than loop induced lepton flavor violation processes, already present in the standard model in the presence of massive neutrinos with mixing. The conclusions of this report lead to lessons concerning flavor mixing, chiral oscillations, interference between positive and negative frequency components of Dirac equation solutions, and the field formulation of quantum oscillations.Comment: 116 pages, 10 figures (The abstract was suppressed due to online title limitations of the abstract field. See the manuscript for obtaining the complete abstract

    Hierarchical genetic structuring in the cool boreal kelp, Laminaria digitata: implications for conservation and management

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    Kelp are foundation species threatened by ongoing warming trends and increased harvesting pressure. This emphasizes the need to study genetic structure over various spatial scales to resolve demographic and genetic processes underpinning resilience. Here, we investigate the genetic diversity in the kelp, Laminaria digitata, in previously understudied southern (trailing-edge) and northern (range-centre) regions in the Northeastern Atlantic Ocean. There was strong hierarchical spatial structuring with significantly lower genetic variability and gene flow among southern populations. As these span the area of the Hurd’s deep Pleistocene glacial refuge, the current low variation likely reflects a fraction of previous levels that has been eroded at the species southern edge. Northern variability and private alleles also indicate contributions from cryptic northern glacial refugia. Contrary to expectations of a positive relationship between neutral genetic diversity and resilience, a previous study reported individuals from the same genetically impoverished southern populations to be better adapted to cope with thermal stress than northern individuals. This not only demonstrates that neutral genetic diversity may be a poor indicator of resilience to environmental stress but also confirms that extirpation of southern populations will result in the loss of evolved, not just potential, adaptations for resilience

    Seasonal development of a tidal mixing front drives shifts in community structure and diversity of bacterioplankton

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    Bacterioplankton underpin biogeochemical cycles and an improved understanding of the patterns and drivers of variability in their distribution is needed to determine their wider functioning and importance. Sharp environmental gradients and dispersal barriers associated with ocean fronts are emerging as key determinants of bacterioplankton biodiversity patterns. We examined how the development of the Celtic Sea Front (CF), a tidal mixing front on the Northwest European Shelf affects bacterioplankton communities. We performed 16S-rRNA metabarcoding on 60 seawater samples collected from three depths (surface, 20 m and seafloor), across two research cruises (May and September 2018), encompassing the intra-annual range of the CF intensity. Communities above the thermocline of stratified frontal waters were clearly differentiated and less diverse than those below the thermocline and communities in the well-mixed waters of the Irish Sea. This effect was much more pronounced in September, when the CF was at its peak intensity. The stratified zone likely represents a stressful environment for bacterioplankton due to a combination of high temperatures and low nutrients, which fewer taxa can tolerate. Much of the observed variation was driven by Synechococcus spp. (cyanobacteria), which were more abundant within the stratified zone and are known to thrive in warm oligotrophic waters. Synechococcus spp. are key contributors to global primary productivity and carbon cycling and, as such, variability driven by the CF is likely to influence regional biogeochemical processes. However, further studies are required to explicitly link shifts in community structure to function and quantify their wider importance to pelagic ecosystems
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