The Synthesis of [{n-Bu2Sn(S2N2)}2] and its use in the preparation of Organometallic Iridium Sulfur Nitrogen Complexes

The addition of [n-Bu2SnCl2] to a solution of [S4N3][Cl] in liquid ammonia gave after extraction of the dry reaction mixture the new tin disulfur dinitrido compound [{n-Bu2Sn(S2N2)}(2)] (1). Reaction of [{n-Bu2Sn(S2N2)}(2)] (1) with the pentamethylcyclopentadienyl (Cp*) iridium derivatives [{IrCl(mu-Cl)(eta(5)-C5Me5)}(2)] or [(eta(5)-C5Me5)IrCl2(PPh3)] gave different products, which were dependent on the reactant ratios. A 1:1 reaction between 1 and [{IrCl(mu-Cl)(eta(5)-C5Me5)}(2)] gave only [(eta(5)-C5Me5)Ir(S2N2)] (2) in moderate yield; the same product in higher yield was obtained from a 2:1 reaction between 1 and [(eta(5)-C5Me5)IrCl2(PPh3)]. Reaction of 1 and [(eta(5)-C5Me5)(2)IrCl2(PPh3)] (1:1 molar ratio) in the presence of NH4[PF6] gave the unusual bimetallic species [(eta(5)-C5Me5)IrCl(PPh3)(S2N2)Ir(eta(5)-C5Me5)][PF6] (3). The X-ray crystal structures of 1, 2, and 3 are reported.PostprintPeer reviewe

Deletion of mtorc1 activity in CD4+ T cells is associated with lung fibrosis and increased γδ T cells

Pulmonary fibrosis is a devastating, incurable disease in which chronic inflammation and dysregulated, excessive wound healing lead to progressive fibrosis, lung dysfunction, and ultimately death. Prior studies have implicated the cytokine IL-17A and Th17 cells in promoting the development of fibrosis. We hypothesized that loss of Th17 cells via CD4-specific deletion of mTORC1 activity would abrogate the development of bleomycin-induced pulmonary fibrosis. However, in actuality loss of Th17 cells led to increased mortality and fibrosis in response to bleomycin. We found that in the absence of Th17 cells, there was continued production of IL-17A by γδT cells. These IL-17A+γδT cells were associated with increased lung neutrophils and M2 macrophages, accelerated development of fibrosis, and increased mortality. These data elucidate the critical role of IL-17A+ γδT cells in promoting chronic inflammation and fibrosis, and reveal a novel therapeutic target for treatment of pulmonary fibrosis

Coronal Temperature Diagnostic Capability of the Hinode/X-Ray Telescope Based on Self-Consistent Calibration

The X-Ray Telescope (XRT) onboard the Hinode satellite is an X-ray imager that observes the solar corona with unprecedentedly high angular resolution (consistent with its 1" pixel size). XRT has nine X-ray analysis filters with different temperature responses. One of the most significant scientific features of this telescope is its capability of diagnosing coronal temperatures from less than 1 MK to more than 10 MK, which has never been accomplished before. To make full use of this capability, accurate calibration of the coronal temperature response of XRT is indispensable and is presented in this article. The effect of on-orbit contamination is also taken into account in the calibration. On the basis of our calibration results, we review the coronal-temperature-diagnostic capability of XRT

β-delayed particle decay of 17ne into p + α + 12C through the isobaric analog state in 17F

We have observed the breakup of the isobaric analog state at 11.193 MeV in 17F into three particles via three channels: proton decay to the α-unbound 9.585 MeV state in 16O; and α decay to the proton-unbound 2.365 and 3.502/3.547 MeV states in 13N. Laboratory α-particle spectra corresponding to these three modes have been generated in Monte Carlo simulations using single-channel, single- and multilevel R-matrix formulas. A fit of these spectra to the α spectrum resulting from a triple-coincidence measurement results in excellent agreement with the experimental spectrum and allows branching ratios to be deduced for these rare decay modes

A bootstrap method for sum-of-poles approximations

A bootstrap method is presented for finding efficient sum-of-poles approximations of causal functions. The method is based on a recursive application of the nonlinear least squares optimization scheme developed in (Alpert et al. in SIAM J. Numer. Anal. 37:1138–1164, 2000), followed by the balanced truncation method for model reduction in computational control theory as a final optimization step. The method is expected to be useful for a fairly large class of causal functions encountered in engineering and applied physics. The performance of the method and its application to computational physics are illustrated via several numerical examples

University-industry relationships and open innovation: Towards a research agenda

Accepted versio

A reassessment of Kelmayisaurus petrolicus, a large theropod dinosaur from the Early Cretaceous of China

The Early Cretaceous fossil record of large−bodied theropods from Asia is poor, hindering comparison of Asian predatory dinosaur faunas with those from other continents. One of the few large Asian theropod specimens from this interval is a partial skull (maxilla and dentary) from the Lianmugin Formation (?Valanginian–Albian), the holotype of Kelmayisaurus petrolicus. Most authors have either considered this specimen as an indeterminate basal tetanuran or a nomen dubium. Weredescribe K. petrolicus and note that it possesses a single autapomorphy (a deep accessory groove on the lateral surface of the anterior dentary), as well as a unique combination of characters that differentiates it from other theropods, affirming its validity. A phylogenetic analysis recovers K. petrolicus as a basal carcharodontosaurid, which is supported by various features: very deep interdental plates (a carcharodontosaurid synapomorphy), fused interdental plates (present in carchardontosaurids and a limited number of other theropods), and the absence of diagnostic features of other clades of large−bodied theropods such as abelisaurids, megalosauroids, and coelurosaurs. As such, Kelmayisaurus is the second known carcharodontosaurid from Asia, and further evidence that this clade represented a global radiation of large−bodied predators during the Early–mid Cretaceous

Photochemically produced SO2 in the atmosphere of WASP-39b

S.-M.T. is supported by the European Research Council advanced grant EXOCONDENSE (no. 740963; principal investigator: R. T. Pierrehumbert). E.K.H.L. is supported by the SNSF Ambizione Fellowship grant (no. 193448). X.Z. is supported by NASA Exoplanet Research grant 80NSSC22K0236. O.V. acknowledges funding from the ANR project ‘EXACT’ (ANR-21-CE49-0008-01), from the Centre National d’Études Spatiales (CNES) and from the CNRS/INSU Programme National de Planétologie (PNP). L.D. acknowledges support from the European Union H2020-MSCA-ITN-2109 under grant no. 860470 (CHAMELEON) and the KU Leuven IDN/19/028 grant Escher. This work benefited from the 2022 Exoplanet Summer Program at the Other Worlds Laboratory (OWL) at the University of California, Santa Cruz, a programme financed by the Heising-Simons Foundation. T.D. is an LSSTC Catalyst Fellow. J.K. is an Imperial College Research Fellow. B.V.R. is a 51 Pegasi b Fellow. L.W. is an NHFP Sagan Fellow. A.D.F. is an NSF Graduate Research Fellow.Photochemistry is a fundamental process of planetary atmospheres that regulates the atmospheric composition and stability1. However, no unambiguous photochemical products have been detected in exoplanet atmospheres so far. Recent observations from the JWST Transiting Exoplanet Community Early Release Science Program2,3 found a spectral absorption feature at 4.05 μm arising from sulfur dioxide (SO2) in the atmosphere of WASP-39b. WASP-39b is a 1.27-Jupiter-radii, Saturn-mass (0.28 MJ) gas giant exoplanet orbiting a Sun-like star with an equilibrium temperature of around 1,100 K (ref. 4). The most plausible way of generating SO2 in such an atmosphere is through photochemical processes5,6. Here we show that the SO2 distribution computed by a suite of photochemical models robustly explains the 4.05-μm spectral feature identified by JWST transmission observations7 with NIRSpec PRISM (2.7σ)8 and G395H (4.5σ)9. SO2 is produced by successive oxidation of sulfur radicals freed when hydrogen sulfide (H2S) is destroyed. The sensitivity of the SO2 feature to the enrichment of the atmosphere by heavy elements (metallicity) suggests that it can be used as a tracer of atmospheric properties, with WASP-39b exhibiting an inferred metallicity of about 10× solar. We further point out that SO2 also shows observable features at ultraviolet and thermal infrared wavelengths not available from the existing observations.Publisher PDFPeer reviewe