15,405 research outputs found

    Cobalt/Organophotoredox Dual-Catalysis-Enabled Cyclization of 1,5,10-Enediynes Involving Metallole-Mediated Remote C(<i>sp</i><sup>3</sup>)–H Bond Activation Leading to Axially Chiral Aryl Alkenes

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    Transition-metal-catalyzed C(sp3)–H functionalization has been much less investigated compared to C(sp2)–H functionalization because the site-selectivity control in C(sp3)–H bond activation is much more challenging than that in C(sp2)–H bond activation. Site-selective C(sp3)–H functionalization without the assistance of directing groups is highly desirable, because the installation and removal of directing groups are not required. Hence, cycloaddition through a site-selective C–H bond activation triggered by the formation of metallacycles, such as metalloles, is a highly atom- and step-economical method for synthesizing complex carbo- and heterocycles from simple unsaturated substrates. Herein, we report the cobalt/photoredox dual-catalysis-enabled cyclization of 1,5,10-enediynes via remote C(sp3)–H bond activation triggered by metallole formation, affording axially chiral aryl alkenes. Several control experiments and theoretical calculations suggest that the C(sp3)–H bond cleavage proceeds through σ-complex-assisted metathesis (σ-CAM) in the metallole intermediate

    Additional file 1 of Pan-cancer assessment of antineoplastic therapy-induced interstitial lung disease in patients receiving subsequent therapy immediately following immune checkpoint blockade therapy

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    Additional file 1: Figure S1. Chest CT images showing preexisting interstitial lung disease (ILD) and drug-induced ILD (DIILD) at the post-ICI setting. Each case number corresponds to that in Table S2. In case 11 (a man with non-small cell lung cancer), CT before initiation of docetaxel therapy following prior durvalumab monotherapy showed localized subpleural reticulation in the lower right lobe (a). CT at the onset of DIILD demonstrated new diffuse ground-glass opacity (GGO) (b). In case 12 (a man with bladder cancer), CT before initiation of enfortumab vedotin therapy following prior pembrolizumab monotherapy showed bilateral peripheral linear shadows with slight GGO (c). CT at the time of DIILD diagnosis showed extensive bilateral areas of GGO and airspace consolidation with traction bronchiectasis (d). In case 14 (a man with esophageal cancer), CT before initiation of docetaxel therapy following prior nivolumab monotherapy showed slight subpleural reticulation and GGO with interlobular septal thickening in the right lower lobe (e). CT image at the onset of DIILD demonstrated multifocal patchy alveolar opacities (f)

    Direct Synthesis of Benzoselenophene and Benzothiophene Derivatives from 1,1-Diarylethenes and Biaryls by Chalcogen Cation-Mediated Successive Bond Formation

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    A Tf2O-mediated sequential C–Se bond-forming reaction of 1,1-diarylethenes and biaryls with methaneselenic acid has been developed. Upon demethylation workup with ethanolamine, the corresponding benzoselenophene derivatives are obtained directly. The related synthesis of benzothiophene derivatives with sodium methanesulfinate is also possible with the unique assistance of the ball milling technique. The active species is considered to be a highly electrophilic chalcogen cation, which enables successive bond formation even at room temperature

    Quantum critical behavior of the hyperkagome magnet Mn3CoSi

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    β-Mn-type family alloys Mn3TX (T = Co, Rh, and Ir; X = Si and Ge) have a three-dimensional antiferromagnetic (AF) corner-shared triangular network, i.e., the hyperkagome lattice. The antiferromagnet Mn3RhSi shows magnetic short-range order over a wide temperature range of approximately 500 K above the Néel temperature TN of 190 K. In this family of compounds, as the lattice parameter decreases, the long-range magnetic ordering temperature decreases. Mn3CoSi has the smallest lattice parameter and the lowest TN in the family. The quantum critical point (QCP) from AF to the quantum paramagnetic state is expected near a cubic lattice parameter of 6.15 Å. Although the Néel temperature of Mn3CoSi is only 140 K, the emergence of the quantum critical behavior in Mn3CoSi is discussed. We study how the magnetic short-range order appears in Mn3CoSi by using neutron scattering, μSR, and bulk characterization such as specific heat capacity. According to the results, the neutron scattering intensity of the magnetic short-range order in Mn3CoSi does not change much at low temperatures from that of Mn3RhSi, although the μSR short-range order temperature of Mn3CoSi is largely suppressed to 240 K from that of Mn3RhSi. Correspondingly, the volume fraction of the magnetic short-range order regions, as shown by the initial asymmetry drop ratio of μSR above TN, also becomes small. Instead, the electronic-specific heat coefficient γ of Mn3CoSi is the largest in this Mn3T Si system, possibly due to the low-energy spin fluctuation near the quantum critical point

    Trends in the Use of Second-Generation Androgen Receptor Axis Inhibitors for Metastatic Hormone-Sensitive Prostate Cancer and Clinical Factors Predicting Biological Recurrence

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    The advent of second-generation androgen receptor axis-targeted agents (ARATs) has revolutionized the treatment of metastatic hormone-sensitive prostate cancer (mHSPC). Biochemical recurrence-free survival (BRFS) was used to compare the efficacy of each ARAT. This multicenter retrospective study included 581 patients with newly diagnosed mHSPC who received first-line hormone therapy. The characteristics of patients treated with different ARATs were compared as well as changes in the usage of each drug over time. For BRFS, the apalutamide (Apa) and enzalutamide (Enza) groups, as well as the abiraterone acetate (Abi) and Apa/Enza groups, were compared. In addition, multivariate analysis was performed to determine predictive factors for biochemical recurrence (BCR). The use of second-generation ARATs tended to increase after May 2020. No significant difference in BRFS was found between patients receiving Apa and Enza (p = 0.490) and those receiving Abi or Apa/Enza (p = 0.906). Multivariate analysis revealed that the neutrophil-to-lymphocyte ratio (NLR) ≥ 2.76 and PSA ≥ 0.550 ng/mL were independent predictors of BCR. There were no significant differences in patient characteristics or BRFS in patients with mHSPC receiving different ARATs as first-line treatment. NLR and PSA may be prognostic factors following the first-line treatment of patients with mHSPC

    Protocol to image deuterated propofol in living rat neurons using multimodal stimulated Raman scattering microscopy

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    Summary: Propofol is a widely used anesthetic important in clinics, but like many other bioactive molecules, it is too small to be tagged and visualized by fluorescent dyes. Here, we present a protocol to visualize deuterated propofol in living rat neurons using stimulated Raman scattering (SRS) microscopy with carbon-deuterium bonds serving as a Raman tag. We describe the preparation and culture of rat neurons, followed by optimization of the SRS system. We then detail neuron loading and real-time imaging of anesthesia dynamics.For complete details on the use and execution of this protocol, please refer to Oda et al.1 : Publisher’s note: Undertaking any experimental protocol requires adherence to local institutional guidelines for laboratory safety and ethics