The photoactivation of electron donor-acceptor complexes has emerged as a sustainable, selective and versatile strategy for the generation of radical species. However, when it comes to aryl radical ...formation, this strategy remains hamstrung by the electronic properties of the aromatic radical precursors, and electron-deficient aryl halide acceptors are required. This has prevented the implementation of a general synthetic platform for aryl radical formation. Our study introduces triarylsulfonium salts as acceptors in photoactive electron donor-acceptor complexes, used in combination with catalytic amounts of newly designed amine donors. The sulfonium salt label renders inconsequential the electronic features of the aryl radical precursor and, more importantly, it is installed regioselectively in native aromatic compounds by C-H sulfenylation. Using this general, site-selective aromatic C-H functionalization approach, we developed metal-free protocols for the alkylation and cyanation of arenes, and showcased their application in both the synthesis and the late-stage modification of pharmaceuticals and agrochemicals.
Magnetic excitations in infinite-layer nickelates Lu, H.; Rossi, M.; Nag, A. ...
Science (American Association for the Advancement of Science),
07/2021, Letnik:
373, Številka:
6551
Journal Article
Recenzirano
Odprti dostop
Looking for magnetic clues
Thin films of the neodymium nickelate NdNiO
2
doped with strontium have recently been found to be superconducting. This materials class bears structural and electronic ...similarities to the famed cuprate superconductors, but how far the analogy goes remains unclear. Lu
et al.
used resonant inelastic x-ray scattering to look for magnetism, which exists in the cuprates, in Nd
1-x
Sr
x
NiO
2
films (see the Perspective by Benckiser). The authors observed magnetic modes in the undoped compound that had a doping evolution consistent with the behavior of a doped Mott insulator.
Science
, abd7726, this issue p.
213
; see also abi6855, p.
157
Resonant inelastic x-ray scattering is used to probe the magnetic excitations in Nd
1−
x
Sr
x
NiO
2
films.
The discovery of superconductivity in infinite-layer nickelates brings us tantalizingly close to a material class that mirrors the cuprate superconductors. We measured the magnetic excitations in these nickelates using resonant inelastic x-ray scattering at the Ni
L
3
-edge. Undoped NdNiO
2
possesses a branch of dispersive excitations with a bandwidth of approximately 200 milli–electron volts, which is reminiscent of the spin wave of strongly coupled, antiferromagnetically aligned spins on a square lattice. The substantial damping of these modes indicates the importance of coupling to rare-earth itinerant electrons. Upon doping, the spectral weight and energy decrease slightly, whereas the modes become overdamped. Our results highlight the role of Mottness in infinite-layer nickelates.
We present results of simulations aimed at tracing the formation of nuclear star clusters (NCs) and black hole (BH) seeds in the framework of the current Λcold dark matter (ΛCDM) cosmogony. These BH ...seeds are considered to be progenitors of the supermassive BHs that inhabit today's galaxies. We focus on two mechanisms for the formation of BHs at high redshifts: as end-products of (1) Population III stars in metal-free haloes, and (2) runaway stellar collisions in metal-poor NCs. Our model tracks the chemical, radiative and mechanical feedback of stars on the baryonic component of the evolving haloes. This procedure allows us to evaluate when and where the conditions for BH formation are met, and to trace the emergence of BH seeds arising from the dynamical channel, in a cosmological context. BHs start to appear already at redshift ∼30 as remnants of Population III stars. The efficiency of this mechanism begins decreasing once feedbacks become increasingly important. Around redshift z∼ 15, BHs mostly form in the centre of mildly metal-enriched haloes inside dense NCs. The seed BHs that form along the two pathways have at birth a mass of around 100-1000 M⊙. The occupation fraction of BHs is a function of both halo mass and mass growth rate: at a given redshift, heavier and faster growing haloes have a higher chance to form a native BH, or to acquire an inherited BH via merging of another system. With decreasing z, the probability of finding a BH shifts towards progressively higher mass halo intervals. This is due to the fact that, at later cosmic times, low-mass systems rarely form a seed, and already formed BHs are deposited into larger mass systems due to hierarchical mergers. Our model predicts that at z= 0, all haloes above 1011 M⊙ should host a BH (in agreement with observational results), most probably inherited during their lifetime. Haloes less massive than 109 M⊙ have a higher probability to host a native BH, but their occupation fraction decreases below 10 per cent.
Agents targeting programmed death-1 receptor (PD-1) and its ligand (PD-L1) are showing promising results in non-small-cell lung cancer (NSCLC). It is unknown whether PD-1/PD-L1 are differently ...expressed in oncogene-addicted NSCLC.
We analysed a cohort of 125 NSCLC patients, including 56 EGFR mutated, 29 KRAS mutated, 10 ALK translocated and 30 EGFR/KRAS/ALK wild type. PD-L1 and PD-1 expression were assessed by immunohistochemistry. All cases with moderate or strong staining (2+/3+) in >5% of tumour cells were considered as positive.
PD-1 positive (+) was significantly associated with current smoking status (P=0.02) and with the presence of KRAS mutations (P=0.006), whereas PD-L1+ was significantly associated to adenocarcinoma histology (P=0.005) and with presence of EGFR mutations (P=0.001). In patients treated with EGFR tyrosine kinase inhibitors (N=95), sensitivity to gefitinib or erlotinib was higher in PD-L1+ vs PD-L1 negative in terms of the response rate (RR: P=0.01) time to progression (TTP: P<0.0001) and survival (OS: P=0.09), with no difference in PD1+ vs PD-1 negative. In the subset of 54 EGFR mutated patients, TTP was significantly longer in PD-L1+ than in PD-L1 negative (P=0.01).
PD-1 and PD-L1 are differentially expressed in oncogene-addicted NSCLC supporting further investigation of specific checkpoint inhibitors in combination with targeted therapies.
We present the results of a semianalytical model that evolves the masses and spins of massive black holes together with the properties of their host galaxies across the cosmic history. As a ...consistency check, our model broadly reproduces a number of observations, e.g., the cosmic star formation history; the black hole mass, luminosity, and galaxy mass functions at low redshift; the black hole-bulge mass relation; and the morphological distribution at low redshift. For the first time in a semianalytical investigation, we relax the simplifying assumptions of perfect coherency or perfect isotropy of the gas fueling the black holes. The dynamics of gas is instead linked to the morphological properties of the host galaxies, resulting in different spin distributions for black holes hosted in different galaxy types. We compare our results with the observed sample of spin measurements obtained through broad K alpha iron line fitting. The observational data disfavor both accretion along a fixed direction and isotropic fueling. Conversely, when the properties of the accretion flow are anchored to the kinematics of the host galaxy, we obtain a good match between theoretical expectations and observations. A mixture of coherent accretion and phases of activity in which the gas dynamics is similar to that of the stars in bulges (i.e., with a significant velocity dispersion superimposed to a net rotation) best describes the data, adding further evidence in support of the coevolution of massive black holes and their hosts.
This article, the fifth in the ACP journal series, presents data evaluated by the IUPAC Subcommittee on Gas Kinetic Data Evaluation for Atmospheric Chemistry. It covers the heterogeneous processes on ...surfaces of solid particles present in the atmosphere, for which uptake coefficients and adsorption parameters have been presented on the IUPAC website in 2010. The article consists of an introduction and guide to the evaluation, giving a unifying framework for parameterisation of atmospheric heterogeneous processes. We provide summary sheets containing the recommended uptake parameters for the evaluated processes. Four substantial appendices contain detailed data sheets for each process considered for ice, mineral dust, sulfuric acid hydrate and nitric acid hydrate surfaces, which provide information upon which the recommendations are made.
ABSTRACT
Several stars detected moving at velocities near to or exceeding the Galactic escape speed likely originated in the Milky Way disc. We quantitatively explore the ‘binary supernova scenario’ ...hypothesis, wherein these ‘hyper-runaway’ stars are ejected at large peculiar velocities when their close, massive binary companions undergo a core-collapse supernova and the binary is disrupted. We perform an extensive suite of binary population synthesis simulations evolving massive systems to determine the assumptions and parameters that most impact the ejection rate of fast stars. In a simulation tailored to eject fast stars, we find the most likely hyper-runaway star progenitor binary is composed of a massive (${\sim}30\, \mathrm{ M}_{\odot }$) primary and an ${\sim}3\!-\!4\, \mathrm{ M}_{\odot }$ companion on an orbital period that shrinks to ≲1 d prior to the core collapse following a common-envelope phase. The black hole remnant formed from the primary must receive a natal kick ≳1000 km s−1 to disrupt the binary and eject the companion at a large velocity. We compare the fast stars produced in these simulations to a contemporary census of early-type Milky Way hyper-runaway star candidates. We find that these rare objects may be produced in sufficient number only when poorly constrained binary evolution parameters related to the strength of post-core-collapse remnant natal kicks and common-envelope efficiency are adjusted to values currently unsupported – but not excluded – by the literature. We discuss observational implications that may constrain the existence of these putative progenitor systems.
Pulmonary carcinoids (PCs) are rare tumors. As there is a paucity of randomized studies, this expert consensus document represents an initiative by the European Neuroendocrine Tumor Society to ...provide guidance on their management.
Bibliographical searches were carried out in PubMed for the terms ‘pulmonary neuroendocrine tumors’, ‘bronchial neuroendocrine tumors’, ‘bronchial carcinoid tumors’, ‘pulmonary carcinoid’, ‘pulmonary typical/atypical carcinoid’, and ‘pulmonary carcinoid and diagnosis/treatment/epidemiology/prognosis’. A systematic review of the relevant literature was carried out, followed by expert review.
PCs are well-differentiated neuroendocrine tumors and include low- and intermediate-grade malignant tumors, i.e. typical (TC) and atypical carcinoid (AC), respectively. Contrast CT scan is the diagnostic gold standard for PCs, but pathology examination is mandatory for their correct classification. Somatostatin receptor imaging may visualize nearly 80% of the primary tumors and is most sensitive for metastatic disease. Plasma chromogranin A can be increased in PCs. Surgery is the treatment of choice for PCs with the aim of removing the tumor and preserving as much lung tissue as possible. Resection of metastases should be considered whenever possible with curative intent. Somatostatin analogs are the first-line treatment of carcinoid syndrome and may be considered as first-line systemic antiproliferative treatment in unresectable PCs, particularly of low-grade TC and AC. Locoregional or radiotargeted therapies should be considered for metastatic disease. Systemic chemotherapy is used for progressive PCs, although cytotoxic regimens have demonstrated limited effects with etoposide and platinum combination the most commonly used, however, temozolomide has shown most clinical benefit.
PCs are complex tumors which require a multidisciplinary approach and long-term follow-up.
This study explores default-mode network (DMN) abnormalities in patients with secondary progressive (SP) and primary progressive (PP) multiple sclerosis (MS) and whether such abnormalities correlate ...with cognitive impairment and damage to selected white matter (WM) fiber bundles, quantified using diffusion tensor (DT) MRI tractography.
Resting state (RS) functional MRI and DT MRI data were acquired from 33 patients with SPMS, 24 patients with PPMS, and 24 controls. Independent component analysis (ICA) was used to identify the DMN. SPM5 was used to assess within- and between-group activations.
Between-group differences in DMN activity were found in the left medial prefrontal cortex (mPFC), left precentral gyrus (PcG), and anterior cingulate cortex (ACC). Compared to controls, patients with SPMS had reduced activity in the mPFC (p = 0.01) and PcG (p = 0.02), while patients with PPMS had reduced activity in the PcG (p = 0.008) and the ACC (p = 0.002). Compared to patients with PPMS, patients with SPMS had increased ACC activity (p = 0.04). Reduction of RS activity in the ACC was more pronounced in cognitively impaired vs cognitively preserved patients with MS (p = 0.02). In patients with MS, DMN abnormalities correlated with the PASAT and word list test scores (r values ranging from 0.35 to 0.45) and DT MRI changes in the corpus callosum and the cingulum (r values ranging from 0.82 to 0.87).
These results suggest that a dysfunction of the anterior components of the default-mode network may be among the factors responsible for the accumulation of cognitive deficits in patients with progressive multiple sclerosis.
Rates of Stellar Tidal Disruption Stone, N. C.; Vasiliev, E.; Kesden, M. ...
Space science reviews,
04/2020, Letnik:
216, Številka:
3
Journal Article
Recenzirano
Tidal disruption events occur rarely in any individual galaxy. Over the last decade, however, time-domain surveys have begun to accumulate statistical samples of these flares. What dynamical ...processes are responsible for feeding stars to supermassive black holes? At what rate are stars tidally disrupted in realistic galactic nuclei? What may we learn about supermassive black holes and broader astrophysical questions by estimating tidal disruption event rates from observational samples of flares? These are the questions we aim to address in this Chapter, which summarizes current theoretical knowledge about rates of stellar tidal disruption, and compares theoretical predictions to the current state of observations.
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