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Free, publicly-accessible full text available June 25, 2024
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Organic trisradicals featuring three-fold symmetry have attracted significant interest because of their unique magnetic properties associated with spin frustration. Herein, we describe the synthesis and characterization of a triangular prism-shaped organic cage for which we have coined the name PrismCage6+ and its trisradical trication—TR3(•+). PrismCage6+ is composed of three 4,4'-bipyridinium dications and two 1,3,5-phenylene units bridged by six methylene groups. In the solid state, PrismCage6+ adopts a highly twisted conformation with close to C3 symmetry as a result of encapsulating one PF6− anion as a guest. PrismCage6+ undergoes stepwise reduction to its mono-, di- and trisradical cations in MeCN on account of strong electronic communication between its 4,4'-bipyridinium units. TR3(•+), which is obtained by reduction of PrismCage6+ employing CoCp2, adopts a triangular prism-shaped conformation with close to C2v symmetry in the solid state. Temperature-dependent continuous-wave and nutation frequency-selective EPR spectra of TR3(•+) in frozen N,N-dimethylformamide indicate its doublet ground state. The doublet-quartet energy gap of TR3(•+) is estimated to be −0.06 kcal mol−1 and the critical temperature of spin-state conversion is found to be ca. 50 K, suggesting that it displays pronounced spin-frustration at the molecular level. To the best of our knowledge, this example is the first organic radical cage to exhibit spin frustration. The trisradical trication of PrismCage6+ opens up new possibilities for fundamental investigations and potential applications in the fields of both organic cages and spin chemistry.more » « lessFree, publicly-accessible full text available June 1, 2024
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Abstract We investigate the structure of the continental lithosphere by combining two approaches: a systematic survey of abrupt changes in seismic properties detected by
P ‐to‐S converted body waves and an integrated geophysical‐petrological inversion for temperature and density in the upper mantle. We refine the global thermo‐chemical model WINTERC‐G in eastern North America by including detailed regional information on the crust into petrological inversions and combine it with the upper mantle layering beneath eastern North America yielded by anisotropy‐aware receiver‐function analysis. Eastern North America's Archean, Proterozoic and Paleozoic lithospheres show an excellent agreement between the depth to the 1,300°C isotherm that bounds the lithosphere and the depth range where converted waves detect abrupt changes in seismic properties. Boundaries with these abrupt changes reside within the rigid mechanical lithosphere and are uncommon in the convecting mantle beneath it. The boundaries include both impedance increases and decreases with depth, as well as anisotropy changes, and must have developed over the course of the assembly and evolution of the lithosphere. In the asthenosphere below, such heterogeneities appear to have been largely mixed out by convection. The existence of abundant interfaces with diverse origin can account for the commonly observed scattered signals from within the continental lithosphere and presents an alternative to the end‐member concept of the mid‐lithospheric discontinuity as a ubiquitous feature with a uniform origin. Generally, we can define continental lithosphere as a region of conductive heat transport and steep geotherm that is characterized by pervasive internal layering of density, elastic moduli and texture. -
Artificial Intelligence (AI) brings advancements to support pathologists in navigating high-resolution tumor images to search for pathology patterns of interest. However, existing AI-assisted tools have not realized the promised potential due to a lack of insight into pathology and HCI considerations for pathologists’ navigation workflows in practice. We first conducted a formative study with six medical professionals in pathology to capture their navigation strategies. By incorporating our observations along with the pathologists’ domain knowledge, we designed NaviPath — a human-AI collaborative navigation system. An evaluation study with 15 medical professionals in pathology indicated that: (i) compared to the manual navigation, participants saw more than twice the number of pathological patterns in unit time with NaviPath, and (ii) participants achieved higher precision and recall against the AI and the manual navigation on average. Further qualitative analysis revealed that participants’ navigation was more consistent with NaviPath, which can improve the examination quality.more » « lessFree, publicly-accessible full text available January 1, 2024
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ABSTRACT We report the detection of ammonia masers in the non-metastable (6, 3), (7, 5), and (6, 5) transitions; the latter being the first unambiguous maser detection of that transition ever made. Our observations include the first very long baseline interferometry detection of ammonia maser emission, which allowed effective constraining of the (6, 5) maser brightness temperature. The masers were detected towards G 358.931−0.030, a site of 6.7-GHz class II methanol maser emission that was recently reported to be undergoing a period of flaring activity. These ammonia masers appear to be flaring contemporaneously with the class II methanol masers during the accretion burst event of G 358.931−0.030. This newly detected site of ammonia maser emission is only the 12th such site discovered in the Milky Way. We also report the results of an investigation into the maser pumping conditions, for all three detected masing transitions, through radiative transfer calculations constrained by our observational data. These calculations support the hypothesis that the ammonia (6, 5) maser transition is excited through high colour temperature infrared emission, with the (6, 5) and (7, 5) transition line ratio implying dust temperatures >400 K. Additionally, we detect significant linearly polarized emission from the ammonia (6, 3) maser line. Alongside our observational and radiative transfer calculation results, we also report newly derived rest frequencies for the ammonia (6, 3) and (6, 5) transitions.
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ABSTRACT We present the results of photometric and spectroscopic monitoring campaigns of the changing look AGN NGC 2617 carried out from 2016 until 2022 and covering the wavelength range from the X-ray to the near-IR. The facilities included the telescopes of the SAI MSU, MASTER Global Robotic Net, the 2.3-m WIRO telescope, Swift, and others. We found significant variability at all wavelengths and, specifically, in the intensities and profiles of the broad Balmer lines. We measured time delays of ∼6 d (∼8 d) in the responses of the Hβ (Hα) line to continuum variations. We found the X-ray variations to correlate well with the UV and optical (with a small time delay of a few days for longer wavelengths). The K-band lagged the B band by 14 ± 4 d during the last three seasons, which is significantly shorter than the delays reported previously by the 2016 and 2017–2019 campaigns. Near-IR variability arises from two different emission regions: the outer part of the accretion disc and a more distant dust component. The HK-band variability is governed primarily by dust. The Balmer decrement of the broad-line components is inversely correlated with the UV flux. The change of the object’s type from Sy1 to Sy1.8 was recorded over a period of ∼8 yr. We interpret these changes as a combination of two factors: changes in the accretion rate and dust recovery along the line of sight.