Charge and Spin Transfer Dynamics in a Weakly Coupled Porphyrin Dimer

The dynamics of electron and spin transfer in the radical cation and photogenerated triplet states of a tetramethylbiphenyl-linked zinc-porphyrin dimer were investigated, so as to test the relevant parameters for the design of a single-molecule spin valve and the creation of a novel platform for the photogeneration of high-multiplicity spin states. We used a combination of multiple techniques, including variable-temperature continuous wave EPR, pulsed proton electron–nuclear double resonance (ENDOR), transient EPR, and optical spectroscopy. The conclusions are further supported by density functional theory (DFT) calculations and comparison to reference compounds. The low-temperature cw-EPR and room-temperature near-IR spectra of the dimer monocation demonstrate that the radical cation is spatially localized on one side of the dimer at any point in time, not coherently delocalized over both porphyrin units. The EPR spectra at 298 K reveal rapid hopping of the radical spin density between both sites of the dimer via reversible intramolecular electron transfer. The hyperfine interactions are modulated by electron transfer and can be quantified using ENDOR spectroscopy. This allowed simulation of the variable-temperature cw-EPR spectra with a two-site exchange model and provided information on the temperature-dependence of the electron transfer rate. The electron transfer rates range from about 10.0 MHz at 200 K to about 53.9 MHz at 298 K. The activation enthalpies Δ‡ H of the electron transfer were determined as Δ‡ H = 9.55 kJ mol–1 and Δ‡ H = 5.67 kJ mol–1 in a 1:1:1 solvent mixture of CD2Cl2/toluene-d 8/THF-d 8 and in 2-methyltetrahydrofuran, respectively, consistent with a Robin–Day class II mixed valence compound. These results indicate that the interporphyrin electronic coupling in a tetramethylbiphenyl-linked porphyrin dimer is suitable for the backbone of a single-molecule spin valve. Investigation of the spin density distribution of the photogenerated triplet state of the Zn-porphyrin dimer reveals localization of the triplet spin density on a nanosecond time scale on one-half of the dimer at 20 K in 2-methyltetrahydrofuran and at 250 K in a polyvinylcarbazole film. This establishes the porphyrin dimer as a molecular platform for the formation of a localized, photogenerated triplet state on one porphyrin unit that is coupled to a second redox-active, ground-state porphyrin unit, which can be explored for the formation of high-multiplicity spin states

Inferring structural variant cancer cell fraction.

We present SVclone, a computational method for inferring the cancer cell fraction of structural variant (SV) breakpoints from whole-genome sequencing data. SVclone accurately determines the variant allele frequencies of both SV breakends, then simultaneously estimates the cancer cell fraction and SV copy number. We assess performance using in silico mixtures of real samples, at known proportions, created from two clonal metastases from the same patient. We find that SVclone's performance is comparable to single-nucleotide variant-based methods, despite having an order of magnitude fewer data points. As part of the Pan-Cancer Analysis of Whole Genomes (PCAWG) consortium, which aggregated whole-genome sequencing data from 2658 cancers across 38 tumour types, we use SVclone to reveal a subset of liver, ovarian and pancreatic cancers with subclonally enriched copy-number neutral rearrangements that show decreased overall survival. SVclone enables improved characterisation of SV intra-tumour heterogeneity

Open Access Solutions for Biodiversity Journals: Don’t Replace One Problem with Another

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Demonstration of reduced neoclassical energy transport in Wendelstein 7-X

Research on magnetic confinement of high-temperature plasmas has the ultimate goal of harnessing nuclear fusion for the production of electricity. Although the tokamak(1) is the leading toroidal magnetic-confinement concept, it is not without shortcomings and the fusion community has therefore also pursued alternative concepts such as the stellarator. Unlike axisymmetric tokamaks, stellarators possess a three-dimensional (3D) magnetic field geometry. The availability of this additional dimension opens up an extensive configuration space for computational optimization of both the field geometry itself and the current-carrying coils that produce it. Such an optimization was undertaken in designing Wendelstein 7-X (W7-X)(2), a large helical-axis advanced stellarator (HELIAS), which began operation in 2015 at Greifswald, Germany. A major drawback of 3D magnetic field geometry, however, is that it introduces a strong temperature dependence into the stellarator's non-turbulent 'neoclassical' energy transport. Indeed, such energy losses will become prohibitive in high-temperature reactor plasmas unless a strong reduction of the geometrical factor associated with this transport can be achieved; such a reduction was therefore a principal goal of the design of W7-X. In spite of the modest heating power currently available, W7-X has already been able to achieve high-temperature plasma conditions during its 2017 and 2018 experimental campaigns, producing record values of the fusion triple product for such stellarator plasmas(3,4). The triple product of plasma density, ion temperature and energy confinement time is used in fusion research as a figure of merit, as it must attain a certain threshold value before net-energy-producing operation of a reactor becomes possible(1,5). Here we demonstrate that such record values provide evidence for reduced neoclassical energy transport in W7-X, as the plasma profiles that produced these results could not have been obtained in stellarators lacking a comparably high level of neoclassical optimization.Previously documented record values of the fusion triple product in the stellarator Wendelstein 7-X are shown to be evidence for reduced neoclassical energy transport in this optimized device

Constraining models for the origin of ultra-high-energy cosmic rays with a novel combined analysis of arrival directions, spectrum, and composition data measured at the Pierre Auger Observatory

The combined fit of the measured energy spectrum and shower maximum depth distributions of ultra-high-energy cosmic rays is known to constrain the parameters of astrophysical models with homogeneous source distributions. Studies of the distribution of the cosmic-ray arrival directions show a better agreement with models in which a fraction of the flux is non-isotropic and associated with the nearby radio galaxy Centaurus A or with catalogs such as that of starburst galaxies. Here, we present a novel combination of both analyses by a simultaneous fit of arrival directions, energy spectrum, and composition data measured at the Pierre Auger Observatory. The model takes into account a rigidity-dependent magnetic field blurring and an energy-dependent evolution of the catalog contribution shaped by interactions during propagation. We find that a model containing a flux contribution from the starburst galaxy catalog of around 20% at 40 EeV with a magnetic field blurring of around 20° for a rigidity of 10 EV provides a fair simultaneous description of all three observables. The starburst galaxy model is favored with a significance of 4.5σ (considering experimental systematic effects) compared to a reference model with only homogeneously distributed background sources. By investigating a scenario with Centaurus A as a single source in combination with the homogeneous background, we confirm that this region of the sky provides the dominant contribution to the observed anisotropy signal. Models containing a catalog of jetted active galactic nuclei whose flux scales with the γ-ray emission are, however, disfavored as they cannot adequately describe the measured arrival directions

AugerPrime surface detector electronics

Operating since 2004, the Pierre Auger Observatory has led to major advances in our understanding of the ultra-high-energy cosmic rays. The latest findings have revealed new insights that led to the upgrade of the Observatory, with the primary goal of obtaining information on the primary mass of the most energetic cosmic rays on a shower-by-shower basis. In the framework of the upgrade, called AugerPrime, the 1660 water-Cherenkov detectors of the surface array are equipped with plastic scintillators and radio antennas, allowing us to enhance the composition sensitivity. To accommodate new detectors and to increase experimental capabilities, the electronics is also upgraded. This includes better timing with up-to-date GPS receivers, higher sampling frequency, increased dynamic range, and more powerful local processing of the data. In this paper, the design characteristics of the new electronics and the enhanced dynamic range will be described. The manufacturing and test processes will be outlined and the test results will be discussed. The calibration of the SD detector and various performance parameters obtained from the analysis of thefirst commissioning data will also be presented

Overview of the first Wendelstein 7-X long pulse campaign with fully water-cooled plasma facing components

After a long device enhancement phase, scientific operation resumed in 2022. The main new device components are the water cooling of all plasma facing components and the new water-cooled high heat flux divertor units. Water cooling allowed for the first long-pulse operation campaign. A maximum discharge length of 8 min was achieved with a total heating energy of 1.3 GJ. Safe divertor operation was demonstrated in attached and detached mode. Stable detachment is readily achieved in some magnetic configurations but requires impurity seeding in configurations with small magnetic pitch angle within the edge islands. Progress was made in the characterization of transport mechanisms across edge magnetic islands: Measurement of the potential distribution and flow pattern reveals that the islands are associated with a strong poloidal drift, which leads to rapid convection of energy and particles from the last closed flux surface into the scrape-off layer. Using the upgraded plasma heating systems, advanced heating scenarios were developed, which provide improved energy confinement comparable to the scenario, in which the record triple product for stellarators was achieved in the previous operation campaign. However, a magnetic configuration-dependent critical heating power limit of the electron cyclotron resonance heating was observed. Exceeding the respective power limit leads to a degradation of the confinement

Search for W´ bosons decaying to a top and a bottom quark at root s=13 TeV in the hadronic final state

A search is performed for W ' bosons decaying to a top and a bottom quark in the all-hadronic final state, in proton-proton collisions at a center-of-mass energy of 13TeV. The analyzed data were collected by the CMS experiment between 2016 and 2018 and correspond to an integrated luminosity of 137fb(-1). Deep neural network algorithms are used to identify the jet initiated by the bottom quark and the jet containing the decay products of the top quark when the W ' boson from the top quark decays hadronically. No excess above the estimated standard model background is observed. Upper limits on the production cross sections of W ' bosons decaying to a top and a bottom quark are set. Both left- and right-handed W ' bosons with masses below 3.4TeV are excluded at 95% confidence level, and the most stringent limits to date on W ' bosons decaying to a top and a bottom quark in the all-hadronic final state are obtained. (C) 2021 The Author(s). Published by Elsevier B.V.Peer reviewe

Search for chargino-neutralino production in events with Higgs and W bosons using 137 fb−1 of proton-proton collisions at √s = 13 TeV

A search for electroweak production of supersymmetric (SUSY) particles in final states with one lepton, a Higgs boson decaying to a pair of bottom quarks, and large missing transverse momentum is presented. The search uses data from proton-proton collisions at a center-of-mass energy of 13 TeV collected using the CMS detector at the LHC, corresponding to an integrated luminosity of 137 fb−1. The observed yields are consistent with backgrounds expected from the standard model. The results are interpreted in the context of a simplified SUSY model of chargino-neutralino production, with the chargino decaying to a W boson and the lightest SUSY particle (LSP) and the neutralino decaying to a Higgs boson and the LSP. Charginos and neutralinos with masses up to 820 GeV are excluded at 95% confidence level when the LSP mass is small, and LSPs with mass up to 350 GeV are excluded when the masses of the chargino and neutralino are approximately 700 GeV. [Figure not available: see fulltext.]. © 2021, The Author(s)